CN109310986A - Particulate water-absorbing agent - Google Patents

Particulate water-absorbing agent Download PDF

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Publication number
CN109310986A
CN109310986A CN201780032929.4A CN201780032929A CN109310986A CN 109310986 A CN109310986 A CN 109310986A CN 201780032929 A CN201780032929 A CN 201780032929A CN 109310986 A CN109310986 A CN 109310986A
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China
Prior art keywords
water
weight
absorbing agent
particulate water
gel
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Granted
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CN201780032929.4A
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Chinese (zh)
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CN109310986B (en
Inventor
鸟井司
鸟井一司
玉置麻利子
高木大辅
堀本裕朗
堀本裕一朗
小林大志
藤本拓
北野贵洋
岩村卓
河田洋辉
后藤宽幸
中嶋康久
池内博之
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3021—Milling, crushing or grinding
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/53—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium
    • A61F2013/530481—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the absorbing medium having superabsorbent materials, i.e. highly absorbent polymer gel materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/68—Superabsorbents

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Public Health (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Engineering & Computer Science (AREA)
  • Epidemiology (AREA)
  • Hematology (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Absorbent Articles And Supports Therefor (AREA)

Abstract

The present invention provides the particulate water-absorbing agent and its manufacturing method for having both high water absorption multiplying power and high water absorption speed.The present invention provides a kind of particulate water-absorbing agent, it is the particulate water-absorbing agent that CRC is 30~50g/g, weight average particle diameter (D50) is 200~600 μm, DRC index shown in the following formula is specific value (such as 43,30 or 20) hereinafter, DRC index (Index of DRC)=(49-DRC5 minutes [g/g])/(D50 [μm]/1000).

Description

Particulate water-absorbing agent
Technical field
The present invention relates to the particulate water-absorbing agents and its manufacturing method that have both high water absorption multiplying power and high water absorption speed.In addition, The present invention relates to the agglomeration for having both high water absorption multiplying power and high water absorption speed, having under super-humid conditions inhibit (hygroscopic fluidity) and/ Or the particulate water-absorbing agent and its manufacturing method of high lower uptake of pressurizeing.
Background technique
Water-absorbing resins (SAP/Super Absorbent Polymer) are that the macromolecule of water-swellable water-insoluble is gelled Agent is used in paper nappy, sanitary napkin, the soil towards the amenities such as adult incontinence product, agriculture and garden The various uses such as earth water-retaining agent, industrial water-stop.This water-absorbing resins propose many monomers, parent as raw material Aqueous high molecular, but from the viewpoint of performance and cost, use acrylic acid and/or its salt as the polyacrylic acid of monomer (salt) water-absorbent resin is most used.
With the high performance of the paper nappy of the main application as water-absorbing resins, water-absorbing resins are required very much Function (physical property).The concrete example of physical property as water-absorbing resins is not limited to simple water absorbent rate high and low level, can enumerate It is gel strength, water soluble ingredient, absorption speed, the lower water absorbent rate that pressurizes, logical fluidity, size distribution, urine patience, antibiotic property, resistance to Impact (traumatic resistance), powder fluidity, smelly eliminating, coloring resistance (whiteness), self raising flour dirt etc..
Patent document 1 (International Publication No. 2011/126079) discloses the water imbibition for having both logical fluidity and absorption speed The manufacturing method and absorbent resin powder of toner.
Patent document 2 (International Publication No. 2015/030129) is disclosed by the system as absorbent resin powder It makes in the gel pulverizing process of one of process, and then uses specific device shape, powder is carried out in a manner of rubbing up aqueous gel It is broken, thus improve water absorbent rate under the pressurization of obtained absorbent resin powder.
Patent document 3 (International Publication No. 2015/030130) is disclosed by the system as absorbent resin powder It makes in the gel pulverizing process of one of process, and then uses specific device shape, powder is carried out in a manner of rubbing up aqueous gel It is broken, thus improve the logical fluidity of obtained absorbent resin powder.
Patent document 4 (International Publication No. 2015/129917) is disclosed by GCA (Gell Capillary ) etc. Absorption the water absorbing agent that the amount of bleeding back of the absorbing articles as defined in actual use reduces.
Patent document 5 (Japanese Unexamined Patent Publication 11-60975 bulletin) is disclosed by for-the COOR with particular range The water-absorbent crosslinked polymers of content and-COOH/-COOR molar ratio (R refers to hydrogen atom, metallic atom or ammonium in formula) are implemented It is surface-crosslinked, the water-absorbing resins for having both high water absorption multiplying power and high water absorption speed can be manufactured.
Technology disclosed in patent document 6 (International Publication No. 2007/004529) is to keep water-soluble olefinic unsaturated single When body carries out inverse suspension polymerization and manufactures water-absorbing resins, the suction of inverse suspension polymerization is carried out with 2 the multistage more than stage The manufacturing method of water-base resin, by adding amino carboxylic acid based compound in the 2nd stage and its at least one later stage Polymerization reaction is carried out, the water-absorbing resins for having both high water absorption multiplying power and high water absorption speed can be manufactured.
Existing technical literature
Patent document
Patent document 1: International Publication No. 2011/126079
Patent document 2: International Publication No. 2015/030129
Patent document 3: International Publication No. 2015/030130
Patent document 4: International Publication No. 2015/129917
Patent document 5: Japanese Unexamined Patent Publication 11-60975 bulletin
Patent document 6: International Publication No. 2007/004529
Summary of the invention
The solution to the problem
The inventors of the present invention further investigate, as a result, it has been found that passing through the crushing (gel powder for increasing the aqueous gel after polymerizeing It is broken) in size reduction energy, the particulate water-absorbing agent for having both high water absorption multiplying power and high water absorption speed can be manufactured, so as to solve Problem.
The inventors of the present invention have found in the various particulate water-absorbing agents of manufacture, research physical property, in weight average particle diameter (D50) and dipping It keeps that linear is shown between the value of capacity 5 minutes (DRC5 minute), the particulate water-absorbing agent as judgement with preferred physical property Index is found DRC index (Index of DRC).In addition, identification provides the particulate water-absorbing agent with preferred DRC index Manufacturing method becomes easy, therefore can manufacture the various particulate water-absorbing agents with preferred physical property.
In addition, the inventors of the present invention have found, by increasing the amount of moisture in the aqueous gel crushed for gel and crushing energy Amount, obtains superior physical property.
The inventors of the present invention in the particulate water-absorbing agent obtained as described above in addition, it is found that by using selected from by with water 2 containing the divalent and trivalent kind metal cation of anatase structure and the multi-element metal compound of hydroxyl and include phosphoric acid class At least one of the group of the water-insoluble metal phosphate of anion and divalent or the metal cation of trivalent composition moisture absorption fluidity Property improver as additive, obtain (being not easy with the high treatability pressurizeed under lower water absorbent rate, and/or super-humid conditions is excellent Generate agglomeration) particulate water-absorbing agent.
In addition, the present invention provides project below.
(project 1)
A kind of particulate water-absorbing agent is the particulate water-absorbing that centrifugal separator keeps capacity (CRC) as 30~50g/g Agent,
Weight average particle diameter (D50) is 200~600 μm,
DRC index shown in the following formula be 43 hereinafter,
DRC index (Index of DRC)=(49-DRC5 minutes [g/g])/(D50 [μm]/1000).
(project 2)
According to particulate water-absorbing agent described in project 1, wherein aforementioned DRC index is 30 or less.
(project 3)
The particulate water-absorbing agent according to any one of project 1~2, wherein aforementioned DRC index is 20 or less.
(project 4)
The particulate water-absorbing agent according to any one of project 1~3, wherein saline flow conductivity (SFC) be 0~ Less than 30 (× 10-7·cm3·s·g-1)。
(project 5)
The particulate water-absorbing agent according to any one of project 1~4, wherein surface tension is 66mN/m or more.
(project 6)
The particulate water-absorbing agent according to any one of project 1~5, wherein grain shape is unsetting broken shape.
(project 7)
The particulate water-absorbing agent according to any one of project 1~6, wherein hygroscopic fluidity (B.R.) is 50 weights Measure % or less.
(project 8)
The particulate water-absorbing agent according to any one of project 1~7, wherein water soluble ingredient (Ext) is 25 weight % Below.
(project 9)
The particulate water-absorbing agent according to any one of project 1~8, wherein deterioration soluble ingredient be 30 weight % with Under.
(project 10)
The particulate water-absorbing agent according to any one of project 1~9, wherein pressurize lower water absorbent rate (AAP) as 18g/ G or more.
(project 11)
The particulate water-absorbing agent according to any one of project 1~10, wherein water absorbent rate (AAP) is under pressurizeing 26g/g or more.
(project 12)
The particulate water-absorbing agent according to any one of project 1~11, wherein air entrapment rate as defined in following formula It is 0.5~2.5%.
(air entrapment rate [%])={ (real density [g/cm3])-(apparent density [g/cm3])/(real density [g/cm3]) ×100
(project 13)
The particulate water-absorbing agent according to any one of project 1~12, wherein bulk density is 0.57~0.75.
(project 14)
The particulate water-absorbing agent according to any one of project 1~13, wherein diffusion absorption multiplying power 60 minutes are 18g/ G or more.
(project 15)
The particulate water-absorbing agent according to any one of project 1~14, wherein diffusion absorption multiplying power 10 minutes are 7g/g More than.
(project 16)
The particulate water-absorbing agent according to any one of project 1~15, by polyacrylic acid (salt) water-absorbent resin As main component.
(project 17)
The particulate water-absorbing agent according to any one of project 1~16 also contains selected from by with hydrotalcite structure 2 containing divalent and trivalent kind metal cation and hydroxyl multi-element metal compound and the anion comprising phosphoric acid class and 2 At least one of the group of the water-insoluble metal phosphate of valence or the metal cation of trivalent composition hygroscopic fluidity improver.
(project 18)
A kind of absorber contains particulate water-absorbing agent described in any one of project 1~17.
(project 19)
A kind of hygienic article contains absorber described in project 18.
(project A1)
A kind of manufacturing method of particulate water-absorbing agent, which is characterized in that for the feature with (1) below~(3) Gel applies the energy of at least one met in following (4)~(5) and carries out gel crushing,
(1) at least the size on 1 side is 3000 μm or more average
(2) gel C RC is 33.0g/g or more
(3) 52 weight % of moisture content or more
It (4) is 20~60J/g as gel size reduction energy (GGE)
It (5) is 9~40J/g as gel size reduction energy (2) (GGE (2)).
(project A2)
According to method described in project A1, which is characterized in that
(a) aforementioned gel is carried out to crush until the partial size of obtained gel is 360~1500 μm,
It (b) in vertical direction (up and down direction) is 0.8~2.5m/s in the wind speed of 150~200 DEG C of drying temperature, hot wind Under the conditions of, the gel weight for belt drying unit area is 10~50kg/m2The gel carry out drying in 10~60 minutes,
(c) it is surface-treated.
(project A3)
The method according to any one of project A1~A2, wherein aforementioned gel size reduction energy (GGE) be 29J/g with On.
(project A4)
The method according to any one of project A1~A3, wherein aforementioned gel size reduction energy (GGE) be 34J/g with On.
(project A5)
The method according to any one of project A1~A4, wherein aforementioned gel size reduction energy (2) (GGE (2)) is 15J/g or more.
(project A6)
The method according to any one of project A1~A5, wherein aforementioned gel size reduction energy (2) (GGE (2)) is 19J/g or more.
(project A7)
The method according to any one of project A1~A6 comprising added relative to 100 parts by weight of water-absorbing resins The process of 0.001~0.2 parts by weight of chelating agent.
(project A8)
The method according to any one of project A1~A7 further includes adding relative to 100 parts by weight of water-absorbing resins Add the process of 0.01~1.0 parts by weight of hygroscopic fluidity improver.
(project A9)
According to method described in project A8, wherein aforementioned hygroscopic fluidity improver be selected from by silica, hydrotalcite, In the group of phosphate and aluminium salt composition.
(project A10)
The method according to any one of project A1~A9, wherein circulation comminution ratio is 1.10~1.50.
(project B1)
A kind of all good method of water absorbent rate and absorption speed for determining particulate water-absorbing agent, this method comprises:
(1) process of the DRC5 minute of the water absorbing agent is measured；
(2) process of the weight average particle diameter (D50) of the water absorbing agent is measured；
(3) it is calculated by the measured value of (1) and (2)
DRC basic index (General Index of DRC)=(K-DRC5 minutes [g/g])/(D50 [μm]/1000)
(here, K is arbitrary constant)
The DRC basic index is to determine there is desired water absorbent rate and absorption speed in specified value situation below Process.
(project C1)
A kind of particulate water-absorbing agent is the particulate water-absorbing that centrifugal separator keeps capacity (CRC) as 30~50g/g Agent meets at least one in (1) below~(5), and in (1)~(5), complete relative to it in the particulate water-absorbing agent Portion amounts to the condition that DRC5 minutes contribution rates account for 60% or more particle satisfaction (1)~(5),
(1) 850~600 μm of partial size of DRC5 minute be 24~44g/g,
(2) 600~500 μm of partial size of DRC5 minute be 29~46g/g,
(3) 500~425 μm of partial size of DRC5 minute be 32~49g/g,
(4) 425~300 μm of partial size of DRC5 minute be 37~53g/g,
(5) 300~150 μm of partial size of DRC5 minute is 41~60g/g.
(project C2)
According to particulate water-absorbing agent described in project C1, wherein aforementioned DRC5 minutes contribution rate is 70% or more.
(project C3)
The particulate water-absorbing agent according to any one of project C1~C2 meets the whole of (2)~(4).
(project C4)
The particulate water-absorbing agent according to any one of project C1~C3 meets the whole of (1)~(5).
(project C5)
The particulate water-absorbing agent according to any one of project C1~C4, wherein saline flow conductivity (SFC) is 0 ~less than 30 (× 10-7·cm3·s·g-1)。
(project C6)
The particulate water-absorbing agent according to any one of project C1~C5, wherein surface tension is 66mN/m or more.
(project C7)
The particulate water-absorbing agent according to any one of project C1~C6, wherein grain shape is unsetting broken shape.
(project C8)
The particulate water-absorbing agent according to any one of project C1~C7, wherein hygroscopic fluidity (B.R.) is 50% Below.
(project C9)
The particulate water-absorbing agent according to any one of project C1~C8, wherein water soluble ingredient (Ext) is 25 weights Measure % or less.
(project C10)
The particulate water-absorbing agent according to any one of project C1~C9, wherein deterioration soluble ingredient is 30 weight % Below.
(project C11)
The particulate water-absorbing agent according to any one of project C1~C10, wherein water absorbent rate (AAP) is under pressurizeing 18g/g or more.
(project C12)
The particulate water-absorbing agent according to any one of project C1~C11, wherein water absorbent rate (AAP) is under pressurizeing 26g/g or more.
(project C13)
The particulate water-absorbing agent according to any one of project C1~C12, wherein the air entrapment as defined in following formula Rate is 0.5~2.5%.
(air entrapment rate [%])={ (real density [g/cm3])-(apparent density [g/cm3])/(real density [g/cm3]) ×100
(project C14)
The particulate water-absorbing agent according to any one of project C1~C13, wherein bulk density is 0.57~0.75.
(project C15)
Polyacrylic acid (salt) is water imbibition tree by the particulate water-absorbing agent according to any one of project C1~C14 Rouge is as main component.
(project C16)
A kind of absorber contains particulate water-absorbing agent described in any one of project C1~C15.
(project C17)
A kind of hygienic article contains absorber described in project C16.
(project D1)
A kind of manufacturing method of particulate water-absorbing agent, which is characterized in that for the feature with (1) below~(2) Gel applies the energy of at least one met in following (3)~(4) and carries out gel crushing,
(1) at least the size on 1 side is 3000 μm or more average
(2) gel C RC is 33.0g/g or more
It (3) is 20~60J/g as gel size reduction energy (GGE)
It (4) is 9~40J/g as gel size reduction energy (2) (GGE (2)).
(project D2)
According to method described in project D1, wherein (5) moisture content of the gel is 50 weight % or more.
(project D3)
The method according to any one of project D1~D2, which is characterized in that
(a) aforementioned gel is carried out to crush until the partial size of obtained gel is 360~1500 μm,
It (b) in vertical direction (up and down direction) is 0.8~2.5m/s in the wind speed of 150~200 DEG C of drying temperature, hot wind Under the conditions of, the gel weight for belt drying unit area is 10~50kg/m2The gel carry out drying in 10~60 minutes,
(c) it is surface-treated.
(project D4)
The method according to any one of project D1~D3, wherein aforementioned gel size reduction energy (GGE) is 20~55J/ g。
(project D5)
The method according to any one of project D1~D4, wherein aforementioned gel size reduction energy (GGE) is 25~50J/ g。
(project D6)
The method according to any one of project D1~D5 comprising added relative to 100 parts by weight of water-absorbing resins The process of 0.001~0.2 parts by weight of chelating agent.
(project D7)
The method according to any one of project D1~D6 further includes adding relative to 100 parts by weight of water-absorbing resins Add the process of 0.01~1.0 parts by weight of hygroscopic fluidity improver.
(project D8)
The method according to any one of project D1~D7, wherein aforementioned hygroscopic fluidity improver is selected from by dioxy In the group that SiClx, hydrotalcite, phosphate and aluminium salt form.
(project D9)
The method according to any one of project D1~D8, wherein circulation comminution ratio is 1.10~1.50.
In the present invention, above-mentioned one or more features it is intended that other than the combination expressed, additionally it is possible to further Combination is to provide.Further embodiment and advantage of the invention is if reading as needed, understanding below be described in detail It can be recognized by one skilled in the art.
The effect of invention
Through the invention, water absorbent rate and water suction compared with the water absorbing agent obtained using previous manufacturing method are developed The excellent particulate water-absorbing agent of both speed.It is obtained in addition, developing through the invention with previous manufacturing method is utilized Water absorbing agent is compared, and both water absorbent rate and absorption speed are excellent, and the agglomeration having under super-humid conditions inhibits (hygroscopic fluidity) And/or the particulate water-absorbing agent of high lower uptake of pressurizeing.
Detailed description of the invention
The measuring instrument that Fig. 1 is DRC5 minutes.In Fig. 1,100 indicate that the supporting cylinder of plastics, 101 indicate stainless steel The wire mesh of 400 mesh, 102 indicate that swell gel, 103 indicate that Petri dish, 104 indicate that glass filter, 105 indicate Filter paper, 106 indicate 0.90 weight % salt water.
Fig. 2 is the cross-sectional of measurement device used in the measurement of diffusion absorption multiplying power.
Fig. 3 is the sectional view of the major part of said determination device.
Fig. 4 be in said determination device, illustrate physiological saline dispersal direction explanatory diagram.
Fig. 5 is DRC5 minute and the weight average particle diameter for drawing the particulate water-absorbing agent of Examples 1 to 23 and comparative example 1~8 (D50) scheme made of.
Specific embodiment
The present invention is illustrated while optimum way described below.In whole this specification, the performance of singular shape As long as no especially referring to, it is construed as the concept also including its plural shape.Therefore article (such as the English of singular shape In the case of " a ", " an ", " the " etc.) as long as no especially referring to, be construed as also include its plural shape concept.In addition, Term used in this specification is construed as using with the meaning usually used in the field as long as no especially referring to. Therefore, have and the present invention as long as no whole buzz word used in other definition then this specification and scientific and technical term The normally understood meaning equivalent in meaning of those skilled in the art.In contradictory situation, this specification (including be defined on It is interior) it is preferential.
[1] definition of term
(1-1) " water-absorbing resins "
" water-absorbing resins " in the present invention refer to the macromolecule gelling agent of water-swellable water-insoluble, refer to meeting The macromolecule gelling agent of following physical property.That is, referring to that satisfaction is as " water-swellable ", the CRC as defined in ERT441.2-02 5g/g or more, and as " water-insoluble ", the macromolecule that the Ext as defined in ERT470.2-02 is 50 weight % physical property below Gelling agent.
Above-mentioned water-absorbing resins can be appropriately designed according to its purposes, is not particularly limited, and preferably makes have carboxyl Unsaturated monomer carries out crosslinked hydrophilic polymers made of cross-linked polymeric.In addition, being not limited to total amount (100 weight %) as polymerization The form of object, in the range of meeting above-mentioned physical property (CRC, Ext), or the water-absorbing resins combination containing additive etc. Object.
In turn, the water-absorbing resins in the present invention are not limited to final products, sometimes referred to as the manufacture work of water-absorbing resins In sequence intermediate (such as aqueous gel shape cross-linked polymer after polymerization, it is dry after dry polymer, it is surface-crosslinked before Absorbent resin powder etc.), merge with above-mentioned water absorbency resin composition, all of which is blanket, being collectively referred to as " water imbibition tree Rouge ".It should be noted that the shape as water-absorbing resins, can enumerate sheet, threadiness, film-form, graininess, coagulate Glue etc., but in the present invention it is preferably granular water-absorbing resins.
(1-2) " particulate water-absorbing agent "
In this specification, water absorbing agent refers to the absorption gelling for making aqueous solution as main component containing water-absorbing resins Agent.In this specification, particulate water-absorbing agent refers to graininess (alias；It is powdered) water absorbing agent, one particulate water-absorbing The aggregate of agent or multiple particulate water-absorbing agents is known as particulate water-absorbing agent." graininess " refers to the form with particle, Grain refer to the solid of size or liquid that can be measured granular wisp (JIS industry parlance voluminous dictionary the 4th edition, Page 2002).It should be noted that particulate water-absorbing agent is only called water absorbing agent sometimes in this specification.
It should be noted that aqueous solution is not limited to water, it can be urine, blood, sweat, excrement, waste liquid, moisture, steam, ice, water With the mixture of organic solvent and/or inorganic solvent, rainwater, underground water etc., it is not particularly limited if comprising water.It can be preferred Enumerate urine, menses, sweat, other body fluid.
Particulate water-absorbing agent of the invention is suitably used as the hygienic material for absorbing aqueous solution.As polymer Water-absorbing resins contain in particulate water-absorbing agent as main component.That is, being preferably comprised in particulate water-absorbing agent In addition to this 60~100 mass %, 70~100 mass %, 80~100 mass %, 90~100 mass % are used as non-polymer, Arbitrarily contain the additives such as water and/or inorganic particles, multivalent metal cation.Preferred moisture content is 0.2~30 mass %. That is, water absorbency resin composition made of the integration of these ingredients is also the scope of particulate water-absorbing agent.
It should be noted that the upper limit of the water-absorbing resins in water absorbing agent is 100 weight % and then 99 mass %, in turn 97 mass %, particularly 95 mass %, 90 weight % or so also contain 0~10 weight % preferably other than water-absorbing resins The ingredient, particularly water, aftermentioned additive (inorganic particles, multivalent metal cation) of left and right.
In addition, the water-absorbing resins as the main component for becoming particulate water-absorbing agent, can enumerate polyacrylic acid (salt) Be resin, polysulfonate sour (salt) be resin, maleic anhydride (salt) be resin, it is Polyacrylamide resin, polyvinyl alcohol resin, poly- Ethylene oxide system resin, poly-aspartate (salt) are that resin, polyglutamic acid (salt) are that resin, polyalginic acid (salt) are resin, form sediment Powder system resin, cellulose-based resin are, it is preferable to use polyacrylic acid (salt) is resin.
(1-3) " polyacrylic acid (salt) "
" polyacrylic acid (salt) " in the present invention refers to polyacrylic acid and/or its salt, refers to containing as main component Have acrylic acid and/or its salt (hereinafter referred to as " acrylic acid (salt) ") as repetitive unit and contain graft content as it is any at The polymer divided.Polyacrylic acid can be obtained by the hydrolysis of polyacrylamide, polyacrylonitrile etc., it is preferred that passing through acrylic acid The polymerization of (salt) obtains.
It should be noted that above-mentioned " main component " refers to the dosage (content) of acrylic acid (salt) relative to making in polymerization Whole monomers (other than internal crosslinking agent), usually the % of 50~100 moles of %, preferably 70~100 moles, more preferably 90~100 moles of %, further preferably substantial 100 moles of %.
(1-4) " EDANA " and " ERT "
" EDANA " is European non-woven fabrics industry meeting (European Disposables and Nonwovens Associations abbreviation), " ERT " are the measuring method (EDANA of the water-absorbing resins of European standard (substantially world standard) Recommended Test Methods) abbreviation.In the present invention, unless otherwise specified then according to ERT (2002 originally Revision/known document), measure the physical property of water-absorbing resins.
(1-4-1)“CRC”(ERT441.2-02)
" CRC " is the abbreviation of Centrifuge Retention Capacity (centrifugal separator holding capacity), is referred to The lower water absorbent rate that do not pressurize (sometimes referred to as " water absorbent rate ") of particulate water-absorbing agent or water-absorbing resins.
Specifically, referring to after particulate water-absorbing agent or water-absorbing resins 0.2g are encased in the fabric bag of nonwoven, soak Stain makes its free swell in 30 minutes in large excess of 0.9 weight % sodium-chloride water solution, then utilizes centrifugal separator (250G) removes the water absorbent rate (unit, g/g) after moisture.
It should be noted that the CRC (hereinafter referred to as " gel C RC ") of aqueous gel shape cross-linked polymer, sample is changed 24 hours are changed to for 0.4g, free swell time to be measured.In addition, in the calculating of the numerical value in measurement, as water suction The weight of property resin, uses the weight of the resin solid content of aqueous gel shape cross-linked polymer.In addition, aqueous gel shape is crosslinked The size on 1 side of polymer be 5mm or more in the case where, cut with scissors etc., form 1mm size below after be measured.
(1-4-2)“AAP”(ERT442.2-02)
" AAP " is the abbreviation of Absorption Against Pressure, refers to particulate water-absorbing agent or water imbibition tree Water absorbent rate under the pressurization of rouge.
Specifically, referring to making particulate water-absorbing agent or water-absorbing resins 0.9g for large excess of 0.9 weight % Sodium-chloride water solution, in 2.06kPa (21g/cm2, 0.3psi) be swollen 1 hour under load after water absorbent rate (unit, g/g). It should be noted that loading condiction is changed to 4.83kPa (49g/cm sometimes2, 0.7psi) measure.
It in addition, being recorded as Absorption Under Pressure in ERT442.2-02, but is essentially in identical Hold.
(1-4-3)“PSD”(ERT420.2-02)
" PSD " is the abbreviation of Particle Size Distribution, refers to measured by sieve classification The size distribution of particulate water absorbent containing or water-absorbing resins.
It should be noted that weight average particle diameter (D50) and the logstandard deviation (σ ζ) of size distribution by with United States Patent (USP) " (3) Mass-Average Particle Diameter (D50) and Logarithmic recorded in No. 7638570 The identical method measurement of Standard Deviation (σ ζ) of Particle Diameter Distribution ".
(1-4-4)“Moisture Content”(ERT430.2-02)
" Moisture Content " refers to the moisture content of water-absorbing resins.
Specifically, referring to by the loss on drying calculating by water-absorbing resins 4.0g when 3 hours dry at 105 DEG C It is worth (unit, weight %).It should be noted that water-absorbing resins are changed to 1.0g sometimes, drying temperature is changed to 180 DEG C and comes It is measured.
(1-4-5)“Ext”(ERT470.2-02)
" Ext " is the abbreviation of Extractables, refers to the water soluble ingredient (water soluble component amount) of water-absorbing resins.
Specifically, refer to making an addition to water-absorbing resins 1.0g into 0.9 weight % sodium-chloride water solution 200ml, with Dissolution amount of polymers (unit, weight %) after 500rpm stirring 16 hours.Dissolve amount of polymers measurement using pH titrate into Row.
(1-5) " dipping keeps being worth for capacity 5 minutes " (DRC5 minutes, Dunk Retention Capacity 5minutes)
Water absorbent rate under not pressurizeing when " DRC5 minutes " refer to 5 minutes.Specifically, referring to inhaling graininess Aqua or water-absorbing resins 1.0g are homogenously dispersed bottom surface with the columnar of mesh in the same manner as the measurement of above-mentioned AAP Slot contacts 5 minutes the water absorbent rate (unit, g/g) after making its free swell with 0.9 weight % sodium-chloride water solution.Measurement side The detailed content of method is recorded in the item of embodiment.
(1-6-1) " DRC basic index "
" DRC basic index " is provided by following formula:
DRC basic index (General Index of DRC)=(K-DRC5 minutes [g/g])/(D50 [μm]/1000).
Here, K is arbitrary constant (such as 49).The value of K can be by manufacturing various particulate water-absorbing agents, measurement DRC5 Minute and D50, determine whether to obtain preferred particulate water-absorbing agent, to be determined as value appropriate.DRC basic index is as judgement The index of particulate water-absorbing agent with preferred physical property is useful.
(1-6-2) " DRC index "
" DRC index " is provided by following formula:
DRC index (Index of DRC)=(49-DRC5 minutes [g/g])/(D50 [μm]/1000).
The case where value for being equivalent to the K of DRC basic index is 49.DRC index and DRC basic index are similarly as judgement The index of particulate water-absorbing agent with preferred physical property is useful.
(1-7) " logical fluidity "
" the logical fluidity " of particulate water-absorbing agent or water-absorbing resins in the present invention refers to leading under load or under non-load The mobility for crossing the liquid between the particle of swell gel, as representative measuring method, there are SFC (Saline Flow Conductivity/ saline flow conductivity), GBP (Gel Bed Permeability/ gel bed permeability).
" SFC " refers to 0.69 weight % chlorination under 2.07kPa load for particulate water-absorbing agent or water-absorbing resins The logical fluidity of sodium water solution, according to the measurement of SFC test method disclosed in U.S. Patent No. 5669894.
" GBP " is deposited is swollen GBP (International Publication No. 2005/016393) or free swell GBP (International Publication under a load No. 2004/096304), evaluate the logical fluidity under the load 70.3psi in 0.9 weight % sodium-chloride water solution.
(1-8) " unsetting broken shape "
Unsetting broken shape is indicated through aqueous gel for the cross-linked polymer in polymerization or after polymerization or its drying Crushed material obtained from object (preferably dried object) is crushed is the particle of shape and revocable broken shape.It is preferably water-soluble Crushed material in liquid polymerization.On the other hand, it in the case where without pulverizing process, typically by inverse suspension polymerization, incites somebody to action The granules for the spherical particle or spherical particle that polymerization of fluid drops such as the spraying, polymerization of polymerized monomer etc. obtain not are unsetting broken Shape.
(1-9) " hygroscopic fluidity "
" hygroscopic fluidity " in the present invention be for by particulate water-absorbing agent in 25 DEG C of temperature and relative humidity 90%RH Under conditions of obtained from agglomeration, conglomeration (caking) or the mobility as powder when placing 1 hour evaluated, lead to Cross " hygroscopic fluidity (B.R.) " (also referred to as Hygroscopic blocking ratio) judgement.The calculating method of hygroscopic fluidity is recorded in implementation in detail Example.Particulate water-absorbing agent is placed on sieve if simple record, is classified, measurement remains on the particulate water-absorbing on sieve The weight (W1 [g]) of agent and the weight (W2 [g]) of the particulate water-absorbing agent by sieve, calculate hygroscopic fluidity according to the following formula.
Hygroscopic fluidity (B.R.) [weight %]={ W1/ (W1+W2) } × 100
The detailed content of measuring method is recorded in the item of embodiment.
(1-10) " hygroscopic fluidity improver "
" hygroscopic fluidity improver " in the present invention refer to by be added to particulate water-absorbing agent or water-absorbing resins, And with addition hygroscopic fluidity improver before compared with improve hygroscopic fluidity compound or composition (B.R. for evaluation inhale Method, the value of B.R. of wet mobility are smaller, mean that hygroscopic fluidity is more excellent).Such as while not wishing to be defined in this, But silica, hydrotalcite, phosphate and aluminium salt can be enumerated.In the present invention, as hygroscopic fluidity improver, it can make With the multi-element metal compound of 2 containing divalent and trivalent kind metal cation and hydroxyl with hydrotalcite structure and comprising The water-insoluble metal phosphate of the metal cation of the anion and divalent or trivalent of phosphoric acid class.
(1-11) " deterioration soluble ingredient "
" deterioration soluble ingredient " in the present invention is referred to through water soluble ingredient (Ext) specified in ERT470.2-02 0.90 mass % sodium-chloride water solution is changed in 0.90 mass % sodium-chloride water solution mixing L-AA by measuring method Made of aqueous solution (deterioration test liquid), 60 DEG C stand 2 hours after stir 1 hour when water soluble ingredient.
(1-12) " gel size reduction energy " (GGE)
When " gel size reduction energy " in the present invention refers to carrying out aqueous gel shape cross-linked polymer gel crushing, coagulate The mechanical energy of Unit Weight required for rubber powder crushing device (Unit Weight of aqueous gel shape cross-linked polymer) do not include By the cooling energy of collet heating, the energy of input water vapour.It should be noted that " gel size reduction energy " is by English " the Gel Grinding Energy " recorded is referred to as " GGE ".GGE is to be driven in gel grinding device by three-phase ac power In the case where dynamic, calculated by following formula (1).
Above-mentioned " power factor " and " motor efficiency " is the device according to variations such as the operating conditions of gel grinding device Intrinsic value, using 0~1 value.These values can be bys inquiry unit manufacturer etc..In addition, gel grinding device passes through In the case that single phase ac is driven by electricity, " √ 3 " in above-mentioned formula can be changed to " 1 " to calculate by GGE.It needs to illustrate It is that the unit for the weight that the unit of voltage is [V], the unit of electric current is [A], aqueous gel shape cross-linked polymer is [g/s]. GGE is measured by the method recorded in International Publication No. 2011/126079.
In addition, being important for the mechanical energy that aqueous gel shape cross-linked polymer applies, therefore excellent in the present invention Current value when subtracting gel grinding device dry run is selected to calculate above-mentioned gel size reduction energy.Especially carried out with a variety of devices In the case that gel crushes, the total of current value when dry run increases, therefore current value when preferably subtracting dry run comes The method of calculating.Gel size reduction energy at this time is calculated by formula below (2).It should be noted that in order to the above-mentioned area GGE Not, GGE (2) are recorded as.
Value when " power factor " and " motor efficiency " in above-mentioned GGE (2) is crushed using gel.It needs to illustrate It is power factor when dry run and for the value of motor efficiency, current value when dry run is possible to small, approximatively It is defined as above-mentioned formula (2)." the aqueous gel shape crosslinking of gel pulverizer is put within 1 second in above-mentioned formula (1) and formula (2) The weight [g/s] of polymer " refers to for example continuously utilizing the feelings of quantitative feeding device supply aqueous gel shape cross-linked polymer Under condition, the value that [g/s] is obtained is scaled if its supply amount is [t/hr].
(1-13) " circulation comminution ratio "
In the present invention, " circulation comminution ratio " passes through the crushing in identical or different pulverizer by following formula subrepresentation Gauge is fixed, passes through crushing quantity [kg/hr] regulation when balance in continuous crushing.
(circulation comminution ratio)=(aggregate supply of particulate water-absorbing agent or water-absorbing resins to pulverizing process)/(dry Total discharge rate of particulate water-absorbing agent or water-absorbing resins in process)
(wherein, (aggregate supply of particulate water-absorbing agent or water-absorbing resins to pulverizing process)=(in drying process Total discharge rate of particulate water-absorbing agent or water-absorbing resins)+(it is supplied again to the classification polymerization of identical or different pulverizing process The amount of object))
Here, effect of the invention is possible to small when small-scale, the regulation of the circulation comminution ratio in the present invention can be upper It states and is suitably applicable in the range of huge size (1 [t/hr]) or more.It recycles comminution ratio and is based on International Publication No. 2011/034146 The method measurement recorded in number.
(1-14)“GCA”(Gel Capillary Absorption)
GCA refers to evaluating forms height between the meniscus of the lower part of the upper surface and Mariotte tube of glass filter Spend the value of 10 minutes liquid absorption capacities in the state of the difference of 10cm.GCA passes through in International Publication No. 2015/129917 The method of record measures.
(1-15) " surface tension "
Surface tension indicates function (free energy) required for increasing the surface area of solid, liquid with per unit area.This Shen Please in so-called surface tension refer to dispersing particulate water-absorbing agent or water-absorbing resins in 0.90 mass % aqueous sodium chloride The surface tension of aqueous solution when in liquid.It is measured by the measuring method recorded in the item of embodiment.
(1-16) " air entrapment rate "
(air entrapment rate [%])={ (real density [g/cm3])-(apparent density [g/cm3])/(real density [g/cm3]) ×100
" real density " in the present invention is referred to for by sufficiently dry (moisture content preferably less than 1 weight %, more preferably Less than polyacrylic acid (salt) water-absorbent resin of 0.5 weight %, particularly preferred less than 0.1 weight %), pass through chemical composition Density (the unit that (micro materials such as high molecular repetitive unit, crosslinking agent, arbitrarily used graft content etc.) uniquely determines； [g/cm3]).Therefore, polyacrylic acid (salt) water-absorbent resin according to its neutralization ratio, the type of salt, (such as rub by neutralization ratio 75 The Sodium Polyacrylate etc. of your %), micro material and find several difference, but approximately fixed value is shown.
On the other hand, " apparent density " in the present invention refers to considering that be present in polyacrylic acid (salt) be water imbibition tree Density (the unit in the gap (also referred to as air entrapment, closed pore bubble) inside the particle of rouge；[g/cm3]).Such as pass through foaming Water-absorbing resins obtained from polymerization, the water-absorbing resins by granulating working procedure inside it exist not with the sky of external connection Between (gap；Air entrapment, closed pore bubble；Close pore).Therefore, the density of water-absorbing resins is surveyed by dry type density measurement In the case where fixed, closing pore cannot be reached due to importing gas, the density measured is by including closing pore (closed pore Bubble) the apparent density that finds out of volume.
(1-17) " bulk density "
Bulk density refers to the density when the vessel filling powder of a constant volume, the internal volume are as volume.Bulk density It is measured by the measuring method recorded in the item of embodiment.
(1-18) " volume average particle size "
" volume average particle size " refers to being averaged for the partial size of volume reference.The volume average particle size of multi-element metal compound The detailed content of measuring method be recorded in the item of embodiment.
(1-19) " crystallite diameter "
Crystallite refers to the maximum set for regarding monocrystalline as, and a grain is made up of multiple crystallites.Crystallite diameter indicates micro- Brilliant diameter (size).Crystallite number if the size of crystallite reduces in 1 grain increases, and the diffraction grating number of each crystallite subtracts It is few.The smaller then diffracted ray of crystallite diameter is wider.It is described in International Publication No. 2015/152299, crystallite diameter is 0.15 μm In the case where above, moisture absorption caking capacity cannot be sufficiently reduced.The detailed content of measuring method is recorded in the item of embodiment.
(1-20) " average primary particle diameter "
The average primary particle diameter of water-insoluble metal phosphate used in the present invention refers to water-insoluble metal tripolyphosphate The specific surface area equivalent spherical diameter of salt.The detailed content of measuring method is recorded in the item of embodiment.
(1-21) " diffusion absorption multiplying power "
Diffusion absorption multiplying power in the present invention refer to considering water-absorbing resins base weight it is high and due to external force and Between the particle of water-absorbing resins it is closely sealed in the state of waterborne liquid extension, absorption for evaluating water-absorbing resins The physics value of amount.Above-mentioned diffusion absorption multiplying power is by beginning to pass through the stipulated time by absorption in the measurement under rated condition Afterwards, such as by calculating after sixty minutes or by measured value after ten minutes.The detailed content of measuring method is recorded in embodiment Item.
(1-22) " amount of bleeding back "
The amount of bleeding back in the present invention refers to that the liquid for being absorbed body absorption is discharged due to applying pressure for absorber Liquid the amount of bleeding back.Also referred to as Re-wet.The detailed content of measuring method is recorded in the item of embodiment.
(1-23) is other
In this specification, indicate that " X~Y " of range refers to " X or more and Y or less ".In addition, as long as no special note It is then referred to as " t (ton) " of the unit of weight " metric ton (Metric ton) ", " ppm " refers to " weight ppm " or " quality ppm".In turn, " weight " and " quality ", " parts by weight " and " mass parts ", " weight % " and " quality % " is respectively as synonym Processing.In addition, "~sour (salt) " refers to "~acid and/or its salt ", " (methyl) acrylic acid " refers to " acrylic acid and/or first Base acrylic acid ".
In addition, being for convenience sometimes recorded as " liter " " l " or " L ", " weight % " is recorded as " wt% ".In turn, into In the case that row micro constitutent measures, detection limit is following to be recorded as N.D (Non Detected).
[2] polyacrylic acid (salt) is the manufacturing method of particulate water-absorbing agent
It is illustrated below for manufacturing process (2-1)~(2-9) of particulate water-absorbing agent of the invention.
The manufacturing process of (2-1) monomer solution
This process is to manufacture to make aqueous solution as main component (hereinafter referred to as " list containing monomer (such as acrylic acid (salt)) Body aqueous solution ") process.It should be noted that in the range of the water absorbing properties of obtained water-absorbing resins will not reduce, Also the slurry liquid of monomer can be used, but in this item, monomer solution is illustrated for convenience.
In addition, above-mentioned " main component " refers to the dosage (content) of acrylic acid (salt) relative to for water-absorbing resins Whole monomers (other than internal crosslinking agent) of polymerization reaction, the usually % or more of 50 moles of % or more, preferably 70 moles, more It is preferred that 90 moles of % or more (upper limit is 100 moles of %).
(acrylic acid)
In the present invention, from the viewpoint of the physical property and productivity of obtained particulate water-absorbing agent, as monomer, preferably Use acrylic acid and/or its salt (hereinafter referred to as " acrylic acid (salt) ").
Above-mentioned " acrylic acid " can be well known acrylic acid, from the polymerism of acrylic acid, the tone of particulate water-absorbing agent Viewpoint consider, can containing as the preferred methoxyl group phenols of polymerization inhibitor, the preferred 200ppm or less of more preferable p methoxy phenol, More preferable 10~160ppm, further preferred 20~100ppm.In addition, U.S. Patent application is public for the impurity in acrylic acid It opens the compound recorded in No. 2008/0161512 and is also applied to the present invention.
In addition, above-mentioned " acrylates " is to neutralize above-mentioned acrylic acid with following alkaline compositions, as the propylene Hydrochlorate, can be commercially available acrylates (such as sodium acrylate), can also in the manufacturing works of particulate water-absorbing agent in and To obtain.
(alkaline compositions)
In the present invention, " alkaline compositions " refer to the composition containing alkali compounds, such as commercially available sodium hydroxide Aqueous solution etc. is suitable.
As above-mentioned alkali compounds, specifically, the carbonate of alkali metal, bicarbonate, alkali metal can be enumerated Hydroxide, ammonia, organic amine etc..Among them, from the viewpoint of the physical property of obtained particulate water-absorbing agent, preferably by force Alkalinity.That is, the hydroxide of the preferably alkali metal such as sodium hydroxide, potassium hydroxide, lithium hydroxide, more preferable sodium hydroxide.
(neutralization)
As the neutralization in the present invention, neutralization (before polymerization) for acrylic acid is can choose or is applied in combination or for will Acrylic acid carries out the neutralization (after polymerization) of aqueous gel shape cross-linked polymer obtained from cross-linked polymeric (hereinafter referred to as " in rear With ") in any one.In addition, these neutralizations can be continous way or intermittent, it is not particularly limited, but is imitated from production The viewpoints such as rate consider to be preferably continous way.
It should be noted that for conditions such as the devices, neutralization temperature, residence time that are neutralized, International Publication No. The condition recorded in No. 2009/123197, U.S. Patent Application Publication No. 2008/0194863 is also applied for the present invention.
For the neutralization ratio in the present invention, relative to the acidic group of monomer, preferably 10~90 moles of %, more preferable 40~85 Mole %, further preferred 50~80 moles of %, particularly preferred 60~75 moles of %.The case where neutralization ratio is less than 10 moles of % Under, water absorbent rate is possible to significantly reduce.On the other hand, in the case which is more than 90 moles of %, it is possible to cannot get Pressurize the high water-absorbing resins of lower water absorbent rate.
Above-mentioned neutralization ratio in rear and in the case where it is also identical.In addition, for the particulate water-absorbing agent as final products Neutralization ratio, be also suitable above-mentioned neutralization ratio.It should be noted that 75 moles of % of neutralization ratio refer to acrylic acid 25 moles of % and third The mixture of 75 moles of % of olefin(e) acid salt.In addition, the mixture is known as acrylate moiety corrective sometimes.
(other monomers)
In the present invention, " other monomers " refers to the monomer other than above-mentioned acrylic acid (salt), can be with acrylic acid (salt) group It closes using manufacturing particulate water-absorbing agent.
As above-mentioned other monomers, water-soluble or hydrophobic unsaturated monomer can be enumerated.Specifically, United States Patent (USP) Application discloses the compound (but other than acrylic acid) recorded in the 2005/0215734th and is also applied for the present invention.
(internal crosslinking agent)
Internal crosslinking agent used in the present invention, the compound recorded in U.S. Patent No. 6241928 are also suitable In the present invention.One kind or two or more compound is selected in view of reactivity among them.
In addition, being considered from viewpoints such as the water absorbing properties of obtained water-absorbing resins, it is preferable to use having polymerism insatiable hunger Compound, the compound more preferably under following drying temperatures with pyrolytic, further preferably tool with group 2 or more Have (poly-) aklylene glycol structural unit has polymerism unsaturated group 2 or more compounds as internal crosslinking agent.
As above-mentioned polymerism unsaturated group, it is preferably listed out that allyl, (methyl) be acrylate-based, more preferable (first Base) it is acrylate-based.In addition, as above-mentioned (poly-) aklylene glycol structural unit, preferably polyethylene glycol, as n number, preferably It is 1~100, more preferable 6~50.
Therefore, it is preferable to use two (methyl) acrylate of (poly-) aklylene glycol or (poly-) aklylene glycol in the present invention Three (methyl) acrylate more preferably use (poly-) ethylene glycol two (methyl) acrylate.
For the dosage of above-mentioned internal crosslinking agent, relative to whole monomers, preferably 0.0001~10 mole of %, more preferably 0.001~1 mole of %.Within the above range by the dosage, desired water-absorbing resins are obtained.It should be noted that In the case that the dosage is very few, there are gel strengths to reduce, the increased tendency of water soluble ingredient, in the case that the dosage is excessive, There are the tendencies that water absorbent rate reduces, therefore not preferably.
In the present invention, preferably it is applicable in and the internal crosslinking agent of specified amount is added to monomer solution in advance, is polymerize The method for carrying out cross-linking reaction simultaneously.On the other hand, it other than the gimmick, can also be added using in polymerization, after polymerization The method of internal crosslinking agent progress post-crosslinking；The method for carrying out radical crosslinking using radical polymerization initiator；Use electronics The method etc. that beam, ultraviolet light isoreactivity energy-ray carry out radiation crosslinking.Alternatively, it is also possible to which these methods are applied in combination.
(other substances for being added to monomer solution)
It, can also be in monomer solution from the viewpoint of the physical property for improving obtained water-absorbing resins in the present invention Manufacture when add following substances.
Specifically, can be with preferably 50 weight % or less, more preferable 20 weight % or less, further preferred 10 weight % Below, particularly preferably 5 weight % or less (lower limit is 0 weight %) addition starch, starch derivatives, cellulose, cellulose are derivative The hydrophilic macromolecules such as object, polyvinyl alcohol, polyacrylic acid (salt), polyacrylic acid (salt) crosslinked, or with preferably 5 weight % with Under, more preferable 1 weight % or less, further preferred 0.5 weight % or less (lower limit be 0 weight %) addition carbonate, azo Close foaming agents, surfactant, chelating agent, the chain-transferring agents such as object, bubble etc..
It, can also be in monomer solution from the viewpoint of the physical property for improving obtained water-absorbing resins in the present invention Manufacture when add alpha-hydroxy carboxylic acid compounds (salt).
(alpha-hydroxy carboxylic acid compounds (salt))
In general, considering from viewpoints such as water absorption character, the tones (preventing from colouring) of obtained water absorbing agent, α-hydroxyl is preferably added Yl carboxylic acid.In addition, the soluble ingredient molecular weight of obtained water absorbing agent reduces, and then is used as and defends by addition alpha-hydroxy carboxylic acid compounds Sticky feeling when green material and unplessantness displeasure reduce, thus from these it is further from the viewpoint of, preferred addition alpha-hydroxy carboxylic acid compounds.It needs It is noted that " alpha-hydroxy carboxylic acid compounds (salt) " refer to intramolecular have in the carboxylic acid of hydroxyl or its salt, α have hydroxyl hydroxyls Yl carboxylic acid or its salt.
As above-mentioned alpha-hydroxy carboxylic acid compounds (salt), specifically, by International Publication No. 2011/040530 " [6] Alpha-hydroxy Compound and its dosage disclosed in carboxylic acid compound " are suitable for the present invention.
Hydroxycarboxylic acid refers to that intramolecular has both the carboxylic acid of hydroxyl, and there are lactic acid, glycolic, malic acid, glyceric acid, winestones The aliphatic hydroxyls such as acid, citric acid, isocitric acid, mevalonic acid, chinic acid, shikimic acid, ethylene lactic acid acid, salicylic acid, wood Evaporate oleic acid, vanillic acid, syringic acid, resorcylic acid, pyrocatechuic acid, protocatechuic acid, gentianic acid, moss, mandelic acid, galla turcica The acid such as aromatic hydroxyls acid such as acid or its salt.
In addition, in the present invention, in the case that alpha-hydroxy carboxylic acid compounds are salt, from the viewpoint of solubility in water, preferably For monovalence salt, it is preferable to use the alkali metal salts such as lithium, potassium, sodium, ammonia salt, monovalence amine salt etc..In addition, Alpha-hydroxy polybasic carboxylic acid is with salt Form use in the case where, can whole carboxyl forming salts, can also be with only a part forming salt.
" alpha-hydroxy carboxylic acid compounds (salt) " refers to alpha-hydroxy carboxylic acid compounds and/or its salt.Similarly "~sour (salt) " refers to~acid And/or its salt.Specifically, malic acid (salt) refers to malic acid and/or its salt, lactic acid (salt) refer to lactic acid and/or its Salt.
In addition, above-mentioned substance not only can be the mode for being added to monomer solution or add in polymerization midway Mode, these modes can also be applied in combination.
It should be noted that in the case where using water-soluble resin or water-absorbing resins, can be obtained as hydrophilic macromolecule To graft polymers or water absorbency resin composition (such as Starch with Acrylic Acid polymer, PVA- acrylate copolymer etc.).These Polymer, water absorbency resin composition are also scope of the invention.
(concentration of monomer component)
In this process, when manufacturing monomer solution, above-mentioned each substance is added.As the monomer component in the monomer solution Concentration, be not particularly limited, but from the viewpoint of the physical property of water-absorbing resins, it is preferably 10~80 weight %, more excellent Select 20~75 weight %, further preferred 30~70 weight %.
In addition, in the case where using aqueous solution polymerization or inverse suspension polymerization, also can according to need be applied in combination water with Outer solvent.At this point, the type for solvent is not particularly limited.
It should be noted that above-mentioned " concentration of monomer component " refers to the value found out using following formula (3), monomer is water-soluble The weight of liquid does not include the weight of graft content, water-absorbing resins, hydrophobic solvent in inverse suspension polymerization.
Formula (3):
(concentration (weight %) of monomer component)=(weight of monomer component)/(weight of monomer solution) × 100
(2-2) polymerization process
This process be make acrylic acid obtained in the manufacturing process of above-mentioned monomer solution (salt) be monomer solution polymerization, The process for obtaining aqueous gel shape cross-linked polymer (hereinafter referred to as " aqueous gel ").
(polymerization initiator)
Polymerization initiator used in the present invention is suitably selected according to polymerization methods etc., therefore is not particularly limited, and can be arranged It enumerates such as heat decomposition type polymerization initiator, photolysis type polymerization initiator or has been applied in combination and promote these polymerization initiators The redox system polymerization initiator of reducing agent of decomposition etc..Specifically, using being disclosed in U.S. Patent No. 7265190 Polymerization initiator in it is one kind or two or more.It should be noted that from the treatability of polymerization initiator, particulate water-absorbing agent or suction It is from the viewpoint of the physical property of water-base resin, it is preferable to use peroxide or azo-compound, more preferable peroxide, further excellent Select persulfate.
For the dosage of the polymerization initiator, relative to monomer, preferably 0.001~1 mole of %, more preferable 0.001~ 0.5 mole of %.In addition, the dosage of the reducing agent is preferably 0.0001~0.02 mole of % relative to monomer.
It should be noted that above-mentioned polymerization initiator can also be substituted, illumination radiation line, electron beam, ultraviolet light isoreactivity Energy-ray implements polymerization reaction, can also be applied in combination these active energy beams and polymerization initiator.
(polymerization methods)
It as polymerization methods are suitable for the invention, is not particularly limited, but is easy from what water absorption character, polymerization controlled Property etc. viewpoints consider, be preferably listed out spray droplet polymerization, aqueous solution polymerization, inverse suspension polymerization, more preferable aqueous solution polymerization, Inverse suspension polymerization, further preferred aqueous solution polymerization.Wherein, particularly preferably continuous aqueous solution polymerization, continuous band polymerization, Any one in continuous kneader polymerization can be applicable in.
As specific polymerization methods, continuous band polymerization is disclosed in U.S. Patent No. 4893999, U.S. Patent No. No. 6241928, U.S. Patent Application Publication No. 2005/215734 etc., continuous kneader polymerization is disclosed in U.S. Patent No. No. 6987151, U.S. Patent No. 6710141 etc..By using these continuous aqueous solution polymerizations, the production of water-absorbing resins is imitated Rate improves.
In addition, the preferred embodiment as above-mentioned continuous aqueous solution polymerization, can enumerate " high temperature causes polymerization ", " high concentration Polymerization "." high temperature cause polymerization " is referred at preferably 30 DEG C or more, more preferable 35 DEG C of temperature or more of monomer solution, into one Cause the mode of polymerization at a temperature of preferably 40 DEG C or more, particularly preferred 50 DEG C of step or more (upper limit is boiling point), " high concentration is poly- Close " refer to monomer concentration preferably 30 weight % or more, more preferable 35 weight % or more, further preferred 40 weight % with The mode that upper, particularly preferred 45 weight % or more (upper limit is saturated concentration) is polymerize.These polymerizations can also be applied in combination Mode.
In addition, can also be polymerize in air atmosphere in the present invention, but from the color of obtained water-absorbing resins From the viewpoint of tune, preferably it is polymerize under the non-active gas atmospheres such as nitrogen, argon gas.At this point, for example preferably by oxygen concentration It is controlled in 1 volume % or less.It should be noted that for the dissolved oxygen in monomer solution, it is also preferred that with non-active gas into Line replacement (such as dissolved oxygen, less than 1mg/l).
In addition, in the present invention, or disperse bubble (especially above-mentioned non-active gas etc.) in monomer solution The foamed polymer being polymerize.
In addition, solid component concentration can be increased in polymerization in the present invention.It is raised as this solid component concentration Index, solid component rise are defined by following formula (4).It should be noted that the rise as the solid component concentration, Preferably 1 weight % or more, more preferable 2 weight % or more.
Formula (4):
(solid component rise (weight %))=(solid component concentration (weight %) of the aqueous gel after polymerization)- (solid component concentration (weight %) of monomer solution)
But the solid component concentration of monomer solution refers to the value found out using following formula (5), in paradigmatic system Ingredient refers to monomer solution and graft content, water-absorbing resins, other solids (such as water insoluble microparticle etc.), does not wrap Include the hydrophobic solvent in inverse suspension polymerization.
Formula (5):
(solid component (weight %) of monomer solution)=((monomer component+graft content+water-absorbing resins+other solid Body object) weight)/(weight of the ingredient in paradigmatic system) × 100
(2-3) gel pulverizing process
This process is to crush such as the screw extruder with kneader, masticator, cutting machine (cutter mill) isogel Aqueous gel obtained in above-mentioned polymerization process is carried out gel crushing, obtains granular aqueous gel (hereinafter referred to as by machine " graininess aqueous gel ") process.It should be noted that in the case that above-mentioned polymerization process is kneader polymerization, while it is real Apply polymerization process and gel pulverizing process.In addition, gas-phase polymerization, inverse suspension polymerization etc. directly obtain particle in the course of the polymerization process In the case where shape aqueous gel, it is possible to not implement the gel pulverizing process.
For gel pulverization conditions other than the above, mode, content disclosed in International Publication No. 2011/126079 exists Reference can be become in the present invention.The detailed content of gel pulverizing process in the present invention is shown in saying for [4] preferred embodiment The manufacturing method of bright (4-3) particulate water-absorbing agent.
(2-4) drying process
This process is that graininess aqueous gel obtained in above-mentioned polymerization process and/or gel pulverizing process is dry to institute Desired resin solid content and the process for obtaining dry polymer.The resin solid content is by loss on drying (by water imbibition tree Weight change when rouge 1g is heated 3 hours at 180 DEG C) it finds out, preferably 80 weight % or more, more preferable 85~99 weight Measure %, further preferred 90~98 weight %, particularly preferred 92~97 weight %.
It as the drying means of above-mentioned graininess aqueous gel, is not particularly limited, such as heat drying, heat can be enumerated Air-dry it is dry, be dried under reduced pressure, fluidized bed drying, infrared drying, microwave drying, drumdrier are dry, utilization and hydrophobicity Drying, high humidity drying that high-temperature vapor is utilized that the azeotropic dehydration of organic solvent carries out etc..Wherein, from the sight of drying efficiency Point consideration, preferably heated-air drying, the belt drying that heated-air drying is more preferably carried out on zone of aeration.
As the drying temperature (temperature of hot wind) in above-mentioned heated-air drying, tone, drying efficiency from water-absorbing resins From the viewpoint of, preferably 120~250 DEG C, 150~200 DEG C more preferable.It should be noted that wind speed, drying for hot wind Drying condition other than the above-mentioned drying temperature such as time, can be according to the moisture content, total for dry graininess aqueous gel The resin solid content of weight and purpose is suitably set, when carrying out belt drying, suitably applicable International Publication No. 2006/100300 Number, International Publication No. 2011/025012, International Publication No. 2011/025013, International Publication No. 2011/111657 etc. The various conditions of middle record.
Within the above range by above-mentioned drying temperature, drying time, obtained water-absorbing resins can be made CRC (centrifugal separator holding capacity), water soluble ingredient (Ext), tone are in desired range (referring to following [4]).
(2-5) pulverizing process, classification process
This process is that dry polymer obtained in above-mentioned drying process is crushed (pulverizing process), is adjusted to prescribed limit Granularity (classification process), obtain absorbent resin powder (for convenience, by implement it is surface-crosslinked before powdered water suction Property resin be known as " absorbent resin powder ") process.
As machine used in pulverizing process of the invention, can enumerate for example open mill, hammer-mill, screw rod grinding machine, (knuckle) type pulverizer, cylinder type mixing machine etc. are touched in the high speeds such as needle mill rotary mill, vibromill, wiping, according to need It is applied in combination.
In addition, being not particularly limited as the particle size adjusting method in classification process of the invention, can enumerate for example makes With sieve classification, the air current classifying etc. of JIS standard screen (JIS Z8801-1 (2000)).It should be noted that water-absorbing resins Granularity adjustment is not limited to above-mentioned pulverizing process, classification process, can pass through polymerization process (especially inverse suspension polymerization, spraying Polymerization of fluid drops), other process (such as granulating working procedure, micro mist recovery process) is appropriately carried out.
For absorbent resin powder obtained in the present invention, as weight average particle diameter (D50), preferably 200~600 μm, More preferable 200~550 μm, it is 250~500 μm further preferred, 350~450 μm particularly preferred.In addition, partial size is less than 150 μm The ratio of particle is preferably 10 weight % or less, more preferable 5 weight % or less, further preferred 1 weight % hereinafter, 850 μ of partial size The ratio of the particle of m or more is preferably 5 weight % or less, more preferable 3 weight % or less, further preferred 1 weight % or less.It needs It is noted that the lower limit value as these particle fractions, all more few the more preferred, preferably 0 weight % in the case of any one, But it may be 0.1 weight % or so.In turn, the logstandard deviation (σ ζ) of size distribution is preferably 0.20~0.50, more It is preferred that 0.25~0.40, further preferred 0.27~0.35.It should be noted that these granularities are according to U.S. Patent No. No. 7638570, measuring method is measured using standard screen disclosed in EDANA ERT420.2-02.
Above-mentioned granularity be applicable not only to it is surface-crosslinked after water-absorbing resins (following sometimes referred to as " water imbibition for convenience Resin particle "), and the particulate water-absorbing agent as final products is also suitable.Therefore, for water-absorbent besin particles and Speech, in order to maintain the granularity of above range, preferably carries out surface-crosslinked processing (surface cross-linking process step), more preferably surface-crosslinked Whole grain process is set after process to adjust granularity.
(2-6) surface cross-linking process step
This process is the superficial layer (table of absorbent resin powder in the absorbent resin powder obtained by above-mentioned operation Face to several 10 μm of parts) process of the high part of crosslink density is set in turn, by mixed processes, heating treatment step and cooling Process is (any) to be constituted.
In the surface cross-linking process step, pass through radical crosslinking, surface aggregate and the surface in absorbent resin powder surface The cross-linking reaction etc. of crosslinking agent, has been carried out surface-crosslinked water-absorbing resins (water-absorbent besin particles).
(surface crosslinking agent)
Surface crosslinking agent used in the present invention, is not particularly limited, and the surface that can enumerate organic or inorganic is handed over Join agent.Wherein, it from the viewpoint of the physical property of water-absorbing resins, the treatability of surface crosslinking agent, is preferably reacted with carboxyl Organic surface crosslinking agent.Surface crosslinking agent one kind or two or more disclosed in such as United States Patent (USP) 7183456 can be enumerated. More specifically, can enumerate polyol compound, epoxide, halogenated epoxide, polyhydric amine compounds or its with The condensation product of halogenated epoxide, oxazoline compound, Oxazolidinone compound, multivalent metal salt, alkylene carbonate esterification Close object, cyclic annular carbamide compound etc..
The dosage (the use of in the case where a variety of being total dosage) of the surface crosslinking agent is relative to 100 weight of absorbent resin powder Measuring part is preferably 0.01~10 parts by weight, more preferable 0.01~5 parts by weight.In addition, the surface crosslinking agent is preferably with aqueous solution Form addition, at this point, the dosage of water relative to 100 parts by weight of absorbent resin powder be preferably 0.1~20 parts by weight, more preferably 0.5~10 parts by weight.And then as needed using in the case where hydrophilic organic solvent, dosage is relative to water-absorbing resins powder Last 100 parts by weight are preferably 10 parts by weight or less, below more preferable 5 parts by weight.
Alternatively, it is also possible to each additive that will add in aftermentioned " humidifying process again " respectively with 5 parts by weight model below It encloses interior mixing, be added to the surface crosslinking agent (aqueous solution), or separately added in this mixed processes.
(mixed processes)
This process is the process for mixing absorbent resin powder and above-mentioned surface crosslinking agent.For the surface crosslinking agent Mixed method is not particularly limited, and can enumerate pre-production surface-crosslinker solution, absorbent resin powder is preferably sprayed Mist is added dropwise the liquid, is sprayed the liquid more preferably come mixed method.
It as the device for carrying out the mixing, is not particularly limited, high-speed stirred type mixing machine, more preferably height is preferably listed out Fast stirred type continuous mixer.
(heating treatment step)
This process is to apply heat, on the surface of absorbent resin powder for the mixture being discharged by above-mentioned mixed processes The process for generating cross-linking reaction.
It is not particularly limited as the device for carrying out the cross-linking reaction, pedal-type dryer is preferably listed out.The cross-linking reaction In reaction temperature, suitably set according to the type of used surface crosslinking agent, it is preferred that for 50~300 DEG C, more preferably 100~200 DEG C.
(cooling process)
This process is any process being set as needed after above-mentioned heating treatment step.
As the device for carrying out the cooling, be not particularly limited, preferably with device phase used in heating treatment step The device of same specification, more preferable pedal-type dryer.This is because, may be used as cooling down by the way that thermophore is changed to refrigerant Device.It should be noted that for water-absorbent besin particles obtained in above-mentioned heating treatment step, in the cooling process, As needed force be cooled to preferably 40~80 DEG C, it is 50~70 DEG C more preferable.
(2-7) humidifies process again
This process is the addition of the water-absorbent besin particles obtained in above-mentioned surface cross-linking process step selected from by following multivalence Metal salt compound, polycationic polymer, chelating agent, inorganic reducing agent, hydroxy carboxylic acid compound, hygroscopic fluidity improve The process of at least one of the group of agent composition additive.
It should be noted that above-mentioned additive is added with aqueous solution or slurry liquid, therefore water-absorbent besin particles water again Swelling.Therefore, this process is known as " humidifying process again ".In addition, as described above, the additive can also with it is above-mentioned surface-crosslinked Agent (aqueous solution) is mixed with absorbent resin powder simultaneously.
(multivalent metal salt and/or cation property copolymer)
In the present invention, from the viewpoint of the raisings such as the absorption speeds of obtained water-absorbing resins, logical fluidity, hygroscopic fluidity Consider, preferably addition multivalent metal salt and/or cation property copolymer.
As above-mentioned multivalent metal salt and/or cation property copolymer, specifically, by International Publication No. 2011/ Compound disclosed in No. 040530 " [7] multivalent metal salt and/or cation property copolymer " and its dosage are suitable for this hair It is bright.
(chelating agent)
In the present invention, from the tones (preventing from colouring) of obtained water-absorbing resins, prevent the viewpoints such as deterioration from considering, preferably Add chelating agent.
As above-mentioned chelating agent, specifically disclosed in " [2] chelating agent " by International Publication No. 2011/040530 Compound and its dosage are suitable for the present invention.
(inorganic reducing agent)
In the present invention, from the tones (preventing from colouring) of obtained water-absorbing resins, prevents deterioration, reduces residual monomer etc. Viewpoint considers, preferably adds inorganic reducing agent.
As above-mentioned inorganic reducing agent, specifically, by International Publication No. 2011/040530 " [3] inorganic reduction Compound and its dosage disclosed in agent " are suitable for the present invention.
(2-8) other additives add process
In the present invention, in order to add various functions for water-absorbing resins, adding other than above-mentioned additive can also be added Add agent.As the additive, specifically, the surfactant, compound with phosphorus atoms, oxidant, organic can be enumerated Organic dusts, deodorant, antibacterial agent, pulp, the thermoplastic fibres such as reducing agent, water-insoluble inorganic particles, metallic soap etc..It needs Illustrate, for above-mentioned surfactant, compound disclosed in International Publication No. 2005/075070 is suitable for this hair It is bright, other above-mentioned water-insoluble inorganic particles, by International Publication No. 2011/040530 " [5] water-insoluble inorganic particles " Disclosed in compound be suitable for the present invention.
The dosage (additive amount) of the additive is suitably determined according to its purposes, therefore is not particularly limited, relative to water suction Property toner 100 parts by weight, below preferably 3 parts by weight, below more preferable 1 parts by weight.In addition, the additive can also be The process addition different from above-mentioned operation.
(2-9) other process
In the present invention, other than above-mentioned operation, granulating working procedure, whole grain process, micro mist can also be set as needed and go Except process, micro mist recycle process etc..Furthermore it is possible to further include conveying operation, storage process, packaging process, keeping process etc. In one kind or two or more process.It should be noted that " whole grain process " includes surface cross-linking process step and its later micro mist Removing step, water-absorbing resins aggregation, more than desired size in the case where the process that is classified, is crushed.In addition, " micro- The recycling process of powder " in addition to as in the present invention directly addition micro mist mode other than, further include to be formed big aqueous gel, It is added to the process of any one process in the manufacturing process of water-absorbing resins.
[3] purposes of particulate water-absorbing agent
The purposes of particulate water-absorbing agent of the invention is not particularly limited, paper nappy, physiology is preferably listed out with defending The absorber purposes of the amenities such as raw towel, incontinence towel.Being particularly useful as foul smell, coloring from raw material etc. becomes problem High concentration paper nappy (dosage of the particulate water-absorbing agent of every 1 paper nappy is more) absorber.In turn, it is used for above-mentioned absorber Upper layer part in the case where, can expect remarkable result.
In addition, other than particulate water-absorbing agent, the absorbabilities material such as pulp fibers also can be used as above-mentioned absorber Material.At this point, the content (core concentration) as the particulate water-absorbing agent in absorber, preferably 30~100 weight %, more preferable 40 ~100 weight %, further preferred 50~100 weight %, even more preferably 60~100 weight %, particularly preferred 70~100 Weight %, most preferably 75~95 weight %.
Within the above range by above-mentioned core concentration, the case where which being used for the upper layer part of absorbent commodity Under, absorbent commodity can keep the white states with clean sense.In turn, since the diffusivity of the body fluid such as urine, blood etc. is excellent It is different, it is improved it is therefore expected that distributing uptake by effective liquid.
[4] explanation of preferred embodiment
It is illustrated below for the preferred embodiment of the present invention.Embodiment presented below is in order to better Understand the present invention and provide, be interpreted as the scope of the present invention not should by it is following record limit.Therefore, art technology It is obvious that personnel can carry out suitably changing with reference to the record in this specification within the scope of the invention.In addition, The following implementation for being interpreted as of the invention can be used alone or combine they come using.
The all good determination method of water absorbent rate and absorption speed of (4-1) particulate water-absorbing agent
The water absorbent rate and all good method of absorption speed for determining particulate water-absorbing agent are provided through the invention.This method Include:
(1) process of the DRC5 minute of the water absorbing agent is measured；
(2) process of the weight average particle diameter (D50) of the water absorbing agent is measured；
(3) it is calculated by the measured value of (1) and (2)
DRC basic index (General Index of DRC)=(K-DRC5 minutes [g/g])/(D50 [μm]/1000)
(here, K is arbitrary constant)
The DRC basic index is to determine there is desired water absorbent rate and absorption speed in specified value situation below Process.Only the DRC5 minute by measurement water absorbing agent and weight average particle diameter (D50), so that it may determine the particle with preferred physical property Shape water absorbing agent.Due to can be determined that the particulate water-absorbing agent with preferred physical property, it will be used to manufacture this preferred graininess and inhale The process most appropriate of aqua also becomes easy.Understand as shown in the examples, by increasing the moisture content of aqueous gel and coagulating Rubber pulverizing energy obtains the particulate water-absorbing agent of excellent physical property.
The value of K in DRC basic index is arbitrary constant.The value of K is, for example, 30,35,40,45,46,47,48,49, 50,51,52,53,54,55,60,70.In one preferred embodiment, the value of K is 49.
Through the invention, obtain having both the particulate water-absorbing agent of high water absorption multiplying power and high water absorption speed (i.e., all good).Think When obtaining having both the particulate water-absorbing agent of high water absorption multiplying power and high water absorption speed, even if (being contained using the raw material of high water absorption multiplying power Hydrogel), the particulate water-absorbing agent of high water absorption speed can not be readily derived.It is formed if not knowing manufacturing process appropriate The particulate water-absorbing agent of such low absorption speed shown in comparative example.The present invention provides the water suction times for determining particulate water-absorbing agent Rate and all good method of absorption speed can be easily found out for obtaining having both high water absorption multiplying power and high water absorption speed Required condition for particulate water-absorbing agent.
The preferred characteristics of (4-2) particulate water-absorbing agent
In one scheme, the present invention provides a kind of particulate water-absorbing agent, be centrifugal separator keep capacity (CRC) be 30~ The particulate water-absorbing agent of 50g/g,
Weight average particle diameter (D50) is 200~600 μm,
DRC index shown in following formula (6) be specific value (such as 43,30 or 20) hereinafter,
Formula (6)
DRC index (Index of DRC)=(49-DRC5 minutes [g/g])/(D50 [μm]/1000).
Above-mentioned formula (6) is to crush various aqueous gels with various gel size reduction energies (GGE), manufacture with various heavy The graininess aqueous gel of partial size D50, research, which have, to be found in the particulate water-absorbing agent of excellent physical property.
The particulate water-absorbing agent for being found to have excellent physical property is obtained by increasing the size reduction energy in gel crushing.This is logical It crosses the particulate water-absorbing agent of the embodiment 6~10 for having used big size reduction energy as shown in embodiment and comparative example and makes It is compared with the comparative example 1~3 of small size reduction energy, shows high DRC5 minute to show.In addition, even if in gel crushing In the case where using big size reduction energy, if weight average particle diameter D50 increase if can also find DRC5 minute reduction (embodiment 6~ 10).Linear is found between D50 and DRC5 minutes.This tendency is in the table 6 for determining second fraction other DRC5 minute In it has also been found that.
As the index for the particulate water-absorbing agent for determining to have preferred physical property, the inventors of the present invention have found above-mentioned formula (6) institute The DRC index (Index of DRC) shown.By the DRC index, it can easily be determined that the graininess with excellent physical property is inhaled Aqua.
DRC index is that the technical meaning of particular value condition below thinks probably as described below.The purpose of the present invention It is, obtains the particulate water-absorbing agent for having both high water absorption multiplying power and high water absorption speed.The molecule of above-mentioned formula (6) is (49-DRC5 points Clock [g/g]), the more big then DRC index of DRC5 minutes values is smaller value.Not pressurizeing when " DRC5 minutes " refer to 5 minutes Under water absorbent rate, it may be said that DRC5 minutes values are reflected as greatly high water absorption speed.K is that the numerical value other than 49 is also identical.
On the other hand, the denominator of above-mentioned formula (6) is (D50 [μm]/1000), and D50 is the weight average particle diameter of particulate water-absorbing agent (being provided by sieve classification).Discovery as described above reduces for DRC5 minutes if D50 increases.It is thought that since only partial size is not With particle group in the case where, if phase homogenous quantities (g) the then small group of partial size, the total specific surface area of unit mass (m2/ g) increase, promptly absorb water.Think in DRC index, by the DRC (g/g) as 5 minutes absorption values divided by D50 (μm)/ 1000 (=weight average particle diameters (unit mm)), offset this influence.In addition, the big particle of partial size is due to needing with diffusion effect Absorption speed is added to consider.Centrifugal separator keeps capacity if comprehensive this influences various as caused by partial size It (CRC) is in the case that 30~50g/g, weight average particle diameter (D50) are 200~600 μm, if being standardized divided by D50 (normalization) then think the physical property for reflecting smashed graininess aqueous gel.
In one preferred embodiment, DRC basic index in K=49, be 43 or less, 42 or less, 41 or less, 40 or less, 39 or less, 38 or less, 37 or less, 36 or less, 35 or less, 34 or less, 33 or less, 32 or less, 31 or less, 30 or less, 29 or less, 28 or less, 27 or less, 26 or less, 25 or less, 24 or less, 23 or less, 22 or less, 21 or less, 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 with Under, 5 or less, 4 or less, 3 or less, 2 or less or 1 or less.K can also similarly calculate numerical value when being other than 49.
The present invention is provided for each partial size by the past no novel manufacturing method by new type of parametric DRC5 of the invention New particulate water absorbing agent as defined in minute etc., the reduction of the new particulate water absorbing agent as defined in DRC5 minutes above-mentioned etc. actually make The amount of bleeding back of the absorbing articles of used time.It is within DRC5 minutes the absorbent properties evaluated in the short time as 5 minutes, for for appropriate The gimmick of absorption speed is evaluated on ground, and evaluation utilizes the pressurization of the absorbent properties under the saturation state of known evaluation 1 hour The characteristic that cannot be suitably evaluated when lower water absorbent rate (AAP), the FHA recorded in U.S. Patent No. 7108916.In addition, specially The GCA recorded in sharp document 4 (International Publication No. 2015/129917) evaluates upper surface and Ma Liaote in glass filter The liquid absorption capacity of " under the pressurization " in 10 minutes in the state of the difference of height 10cm is formed between the meniscus of the lower part of pipe. It is within DRC5 minutes the parameter of the absorbent properties under " not the pressurizeing " evaluated as 5 minutes in the further short time.GCA and DRC5 Minute is the parameter that cannot analogize evaluation mutually due to determination condition difference.In addition, DRC5 minutes more suitable in paper nappy Locality evaluation absorbs the absorbability of urine by pulp and then chafing, urine is inhibited to leak.
Polyacrylic acid obtained in the present invention (salt) is particulate water-absorbing agent, which is being used for hygienic use In the case where product, particularly paper nappy, it is preferred that by following physical property shown, it is at least one above, preferably include AAP And/or including B.R. two or more, more preferably 3 kinds or more including AAP and/or B.R. including, most preferably whole physical characteristics control In in desired range.In the case that these physical property are unsatisfactory for following ranges, effect of the invention cannot be sufficiently obtained, in height It is possible to that abundant performance cannot be played in concentration paper nappy.DRC index is particular value (such as 43,30 or 20) present invention below Particulate water-absorbing agent be in desired range for any or all of in these physical property.
In addition, the polyacrylic acid (salt) obtained through the invention is that particulate water-absorbing agent does not limit its shape especially It is fixed, it is preferred that being graininess.In this item, for particulate water-absorbing agent or water-absorbing resins, illustrate its physical property.It needs to illustrate It is that following physical property are then measured according to EDANA method unless otherwise specified.
DRC5 minutes (dipping keeps being worth for capacity 5 minutes)
It is not particularly limited if the DRC5 minute of particulate water-absorbing agent of the invention meets above-mentioned DRC index, but it is excellent It is selected as 35g/g or more, 38g/g or more, 40g/g or more.The upper limit is also not particularly limited, usually 60g/g or less, 55g/ G or less.
CRC (centrifugal separator holding capacity)
The CRC (centrifugal separator holding capacity) of particulate water-absorbing agent of the invention is 30~50g/g, preferably 31~50g/ G, 32~50g/g, 33~50g/g, 34~50g/g, 35~50g/g, 36~50g/g, 30~49g/g, 30~48g/g, 30~ 47g/g, 30~46g/g, 30~45g/g, 30~44g/g, 30~43g/g, 30~42g/g, 30~41g/g, 30~40g/g, 30~39g/g, 30~38g/g.
In the case that the CRC is less than 5g/g, uptake is few, and the absorber as amenities such as paper nappys is improper 's.In addition, the speed for absorbing body fluid such as urine, blood etc. reduces, therefore is not suitable for high suction in the case that the CRC is more than 70g/g The paper nappy etc. of water speed type.It should be noted that CRC can be controlled by internal crosslinking agent, surface crosslinking agent etc..
Granularity (size distribution, weight average particle diameter (D50), size distribution logstandard deviation (σ ζ))
For particulate water-absorbing agent of the invention granularity (size distribution, weight average particle diameter (D50), size distribution logarithm Standard deviation (σ ζ)) controlled with implement it is surface-crosslinked before the granularity of absorbent resin powder it is identical.It is preferred that as above It states (2-5) pulverizing process, be classified in process described in record.
Saline flow conductivity (SFC)
The saline flow conductivity (SFC) preferably less than 30 (× 10 of particulate water-absorbing agent of the invention-7·cm3·s·g-1), more preferably less than 25 (× 10-7·cm3·s·g-1), more preferably less than 20 (× 10-7·cm3·s·g-1), especially Preferably less than 15 (× 10-7·cm3·s·g-1)。
Surface tension
The surface tension (passing through the measurement law regulation recorded in embodiment) of particulate water-absorbing agent of the invention is preferably 66mN/m or more, preferably 67mN/m or more, more preferable 68mN/m or more, further preferred 69mN/m or more, further preferably 70mN/m or more, particularly preferred 71mN/m or more, most preferably 72mN/m or more, also not substantial surface tension reduces.On Limit is usually that 75mN/m is sufficient.
Meet above-mentioned condition by surface tension, the amount of bleeding back in paper nappy can be reduced.
In one preferred embodiment, the grain shape of particulate water-absorbing agent of the invention is unsetting broken shape.This be by In, compared with the spherical particle obtained by inverse suspension polymerization, gas-phase polymerization, when unsetting broken shape, large specific surface area, because The absorption speed of this particulate water-absorbing agent increases, and is also readily secured to pulp.
Hygroscopic fluidity (Hygroscopic blocking ratio) (B.R.)
Measurement (evaluation) method of specific hygroscopic fluidity (B.R.) is recorded in the item of embodiment, graininess of the invention The hygroscopic fluidity (B.R.) of water absorbing agent be usually 50 weight % or less, preferably 40 weight % or less, more preferable 30 weight % with Under, further preferred 20 weight % or less, still more preferably 10 weight % or less, most preferably 0 weight %.In addition, of the invention Particulate water-absorbing agent hygroscopic fluidity (B.R.) can for 0~50 weight %, 0~40 weight %, 0~30 weight %, 0~ 20 weight % or 0~10 weight %.In the case that above-mentioned hygroscopic fluidity (B.R.) is more than 50 weight %, under how wet environment, The treatability of particulate water-absorbing agent is deteriorated, when the manufacture of the thin absorbent body towards hygienic material etc., it is possible to produce manufacture work Aggregation and the generation of blocking, the problems such as cannot uniformly being mixed with hydrophilic fibre in the transfer piping of factory.
By meeting above-mentioned condition, when using particulate water-absorbing agent and fiber base material production absorber, it is possible to reduce to dress Install standby attachment.
In one preferred embodiment, the water soluble ingredient (Ext) of particulate water-absorbing agent of the invention be 25 weight % or less, It is preferred that 24 weight % or less, more preferable 22 weight % or less, further preferred 20 weight % or less.By meeting above-mentioned condition, The absorbability (such as the lower water absorbent rate etc. that pressurizes) of particulate water-absorbing agent improves, therefore above-mentioned particulate water-absorbing agent is used for paper When diaper, the performances such as Re-wet can be improved.
In one preferred embodiment, the deterioration soluble ingredient of particulate water-absorbing agent of the invention is 30 weight % or less, excellent Select 27 weight % or less, more preferable 24 weight % or less, further preferred 20 weight % or less.By meeting above-mentioned condition, The urine patience of particulate water absorbent containing improves, therefore when above-mentioned particulate water-absorbing agent is used for paper nappy, can inhibit due to bodies such as urine Gel collapse caused by liquid, pachylosis, chafing, stench removal ability reduce the problems such as.
Pressurize lower water absorbent rate (AAP)
Water absorbent rate (AAP) is preferably 18g/g or more, more preferable 22g/g under the pressurization of particulate water-absorbing agent of the invention Above, further preferred 24g/g or more, particularly preferred 26g/g or more, further particularly preferred 28g/g or more, most preferably 30g/ G or more.Upper limit value is not particularly limited, it is preferred that being 40g/g or less.
In the case that the AAP is less than 18g/g, the amount of bleeding back of liquid when for absorber application pressure is (commonly referred to as " Re-Wet (bleeding back) ") increase, the absorber as amenities such as paper nappys is inappropriate.It should be noted that AAP can To pass through the control such as granularity, surface crosslinking agent.
By meeting above-mentioned condition, the paper nappy manufactured using above-mentioned particulate water-absorbing agent is absorbed the absorption of urine by paper pulp Ability is excellent, can reduce the amount of bleeding back, and can inhibit chafing, urine leakage.
Air entrapment rate
The air entrapment rate of particulate water-absorbing agent of the invention is 0.5~2.5%, preferably 0.8~2.3%, more preferable 1.0 ~2.0%.By the way that air entrapment rate to be controlled in above range, obtain that there is absorption speed and logical liquid specified in the present invention The water-absorbing resins of property.Air entrapment rate can gel size reduction energy, water soluble ingredient in manufacturing method through the invention The control such as increasing degree of molecular weight, the gimmicks such as foaming when in addition can also use (being applied in combination) foamed polymer, dry.
While not wishing to be bound by theory, but it is in the range of above-mentioned value by air entrapment rate, suction can be had both The logical fluidity and absorption speed of aqua.
Bulk density
The bulk density of particulate water-absorbing agent of the invention is 0.57~0.75 [g/cm3], preferably 0.58~0.74 [g/cm3]、 More preferable 0.59~0.73 [g/cm3], further preferred 0.60~0.72 [g/cm3]。
Diffusion absorption multiplying power
Diffusion absorption multiplying power 60 minutes of particulate water-absorbing agent of the invention be preferably 18g/g or more, more preferable 20g/g with Upper, most preferably 22g/g or more.Generally go through diffusion absorption multiplying power 60 minutes of the absorbent of surface-crosslinked processing for 18g/g with On, but also 60 minutes low water absorbing agents of rare diffusion absorption multiplying power.If diffusion absorption multiplying power 60 minutes it is low if in absorber Diffusivity is deteriorated, even if DRC, DRC index are excellent, it is also possible to cannot give full play to the performance as absorber.For the upper limit It is not particularly limited, usually the left and right 40g/g or less.
Diffusion absorption multiplying power 10 minutes of particulate water-absorbing agent of the invention be preferably 7g/g or more, more preferable 9g/g with Upper, further preferred 11g/g or more, most preferably 13g/g or more.Generally go through the diffusion absorption of the water absorbing agent of surface-crosslinked processing It is 7g/g or more, but also seldom there is 10 minutes low water absorbing agents of diffusion absorption multiplying power within multiplying power 10 minute.If diffusion absorption times Diffusivity in rate 100 minutes low then absorbers is deteriorated, even if DRC, DRC index are excellent, it is also possible to cannot give full play to work For the performance of absorber.The upper limit is not particularly limited, usually the left and right 30g/g or less.
Yellow chromaticity (YI value/Yellow Index)
Yellow chromaticity (YI value/Yellow Index/ is referring to European patent 942014 and European patent 1108745) is preferably 0~17, more preferable 0~16, further preferred 0~15, most preferably 0~14 is shown, preferably almost without band yellow.For tone Measuring method, the method (Lab value, YI value, WB value etc.) recorded in International Publication No. 2009/005114 can be exemplified.
By meeting above-mentioned condition, particulate water-absorbing agent and white pulp when Composite, can manufacture in hygienic material The paper nappy of foreign body sensation caused by will not providing coloring.
In one preferred embodiment, the coloring of particulate water-absorbing agent of the invention promotes (70 DEG C, 65RH%, 1 after test Week) YI value be 35 or less, preferably 30 or less, more preferable 25 or less, further preferred 22 or less.By meeting above-mentioned condition, Particulate water-absorbing agent and white pulp when Composite, can manufacture different caused by will not providing coloring in hygienic material The paper nappy of object sense.
GCA(Gel Capillary Absorption)
The value of the GCA of particulate water-absorbing agent of the invention is calculated by the method recorded in aftermentioned embodiment, and value is got over It is high then indicate that performance is more excellent, it is 27.0g/g or more, 28g/g or more, 29g/g or more, 30.0g/g or more, 31g/g or more. The the upper limit of GCA the high then the more preferred, but from the viewpoint of being balanced with other physical property, it is often preferred that the left and right 50.0 [g/g].
By meeting above-mentioned condition, the absorption that urine is absorbed by pulp of the paper nappy manufactured using above-mentioned particulate water-absorbing agent Ability is excellent, can reduce the amount of bleeding back, and can inhibit chafing, urine leakage.
In one preferred embodiment, the traumatic resistance coating that particulate water-absorbing agent of the invention illustrates in embodiment is mixed In machine (paint shaker) test, the incrementss for the particle with 150 μm of partial sizes below that test front and back generates are+5% Below, preferably+4% or less, more preferably+3% or less, further preferably+2% or less, even more preferably+1% or less.
The amount of bleeding back
The amount of bleeding back of the absorber made using particulate water-absorbing agent of the invention is preferably 14g or less, further preferably 13.5g or less, 13g or less, 12.5g or less, 12g or less, 11.5g or less, 11g or less, 10.5g or less, 10g or less, 9.5g Below, 9g or less, 8.5g or less, 8g or less, 7.5g or less, 7g or less, 6.5g or less, 6g or less, 5.5g or less, 5g or less, 4.5g or less, 4g or less, 3.5g or less, 3g or less, 2.5g or less.
In one preferred embodiment, physical property and productivity of the above-mentioned particulate water-absorbing agent from obtained particulate water-absorbing agent From the viewpoint of, using polyacrylic acid (salt) water-absorbent resin as main component.
In one scheme, the present invention provides a kind of particulate water-absorbing agent, wherein it is 30 that centrifugal separator, which keeps capacity (CRC), ~50g/g,
Weight average particle diameter (D50) is 200~600 μm,
DRC index shown in following formula (6) be specific value (such as 43,30 or 20) hereinafter,
Formula (6)
DRC index (Index of DRC)=(49-DRC5 minutes [g/g])/(D50 [μm]/1000),
The particulate water-absorbing agent contain selected from by with hydrotalcite structure 2 containing divalent and trivalent kind metal cation and The multi-element metal compound and anion and divalent comprising phosphoric acid class of hydroxyl or the water-insoluble gold of the metal cation of trivalent Belong at least one of the group of phosphate composition hygroscopic fluidity improver.
The present invention provides other than having both high water absorption multiplying power and high water absorption speed (i.e., good), also realizes high wet bar Agglomeration under part inhibits the particulate water-absorbing agent of (hygroscopic fluidity) and/or high lower uptake of pressurizeing.Hygroscopic fluidity (B.R.) In the case where more than 50 weight %, under how wet environment, the treatability of particulate water-absorbing agent is deteriorated, towards the thin of hygienic material When the manufacture of type absorber etc., it is possible to produce manufacturing works transfer piping in aggregation and blocking generation, cannot be with parent The problems such as aqueous fiber uniformly mixes.In the case that absorbent rate under pressure (AAP) is less than 18g/g, absorber is applied and is pressed The amount of bleeding back (commonly referred to as " Re-Wet (bleeding back) ") of liquid when power increases, and the absorber as amenities such as paper nappys is It is inappropriate.The present invention passes through containing selected from by 2 containing divalent and trivalent kind metal cation and hydroxyl with hydrotalcite structure The multi-element metal compound and anion and divalent comprising phosphoric acid class of base or the water-insoluble metal of the metal cation of trivalent At least one of the group of phosphate composition hygroscopic fluidity improver can provide the agglomeration realized under super-humid conditions and inhibit The particulate water-absorbing agent of (hygroscopic fluidity) and/or high lower uptake of pressurizeing.
The multi-element metal compound of 2 containing divalent and trivalent kind metal cation and hydroxyl with hydrotalcite structure
In the present invention, particulate water-absorbing agent can contain 2 containing the divalent and trivalent kind metal sun with hydrotalcite structure The multi-element metal compound of ion and hydroxyl is as hygroscopic fluidity improver.For multi-element metal compound of the invention, inhale The reduction of the water absorbing properties such as the AAP of aqua is small, has both the function of inhibiting moisture absorption agglomeration.
Multi-element metal compound of the invention has neatly known to the structure as lamellar compound shown in general formula (7) Stone spline structure,
[M1 2+ 1-xM2 3+ x(OH-)2]x+·[(An-)x/n·mH2O]x-(M1 2+Indicate divalent metal cation, M2 3+Indicate trivalent gold Belong to cation, An-Indicate n valence anion, H2O indicates water).
As divalent metal cation, Mg can be enumerated2+、Fe2+、Zn2+、Ca2+、Ni2+、Co2+、Cu2+, seen from heat resistance etc. Point consideration, preferably Mg2+.As aforementioned trivalent metal cation, Al can be enumerated3+、Fe3+、Mn3+, examined from viewpoints such as heat resistances Consider, preferably Al3+.Therefore, in a preferably embodiment for multi-element metal compound, divalent metal cation is magnesium cation, 3 Valence metal cation is aluminium cations.
In addition, for the ratio of divalent metal cation and trivalent metal cation in general formula (7), preferably x is in 0.2~ In the range of 0.75, in the range of being more preferably in 0.25~0.7, further preferably in the range of 0.25~0.5.Separately Outside, as anion, OH can be enumerated-、F-、Cl-、Br-、NO3 -、CO3 2-、SO4 2-、Fe(CN)6 3-、CH3COO-, oxalate denominationby Or Salicylate ion etc., it is preferred that being carbonate anion.In addition, m is the real number greater than 0, preferably 0 < m≤10.
The shape of multi-element metal compound is not particularly limited, can be spherical (including powdered).In addition, polynary Metallic compound can be certain granularity, and volume average particle size can be 2 μm or less, can be 1.5 μm or less, can be 1 μ M or less.If partial size increase if in order to obtain sufficient dust reducing effect and need many additive amounts, result is possible to damage The water absorbing properties of obtained water absorbing agent.Workability reduces or cannot get abundant performance when there is addition process if too small Possibility, therefore volume average particle size can be 0.05 μm or more, can be 0.1 μm or more, can be 0.3 μm or more.It needs Illustrate, the volume average particle size of multi-element metal compound can use " laser diffraction scattering method " and (such as be filled using day machine Corporation, trade name: the measurement of Microtrac MT3000II grain size analysis meter) measurement.In addition, being attached to water-absorbing resins surface Multi-element metal compound average grain diameter measurement can by the method recorded as embodiment use SEM (scanning Electron microscope) measuring method measurement.
In turn, (intercalation) organic compound can be inserted in interlayer, also can be implemented for raising and resin Deng Combination surface treatment.
As the preferred structural formula of multi-element metal compound, Mg can be enumerated6Al2(OH)16CO3·4H2O、Mg4Al2 (OH)12CO3·3H2O、Mg4.5Al2(OH)13CO3·3.5H2O etc., specifically, Kyowa Chemical Industry Co., Ltd can be enumerated DHT-4H, DHT-6 of system, the STABIACE HT-1-NC of Sakai Chemical Industry Co., Ltd., STABIACE HT-P etc..
Whether there is or not surface treatments to be ok for hydrotalcite compound (HT compound), but more preferably without by surface treatment HT compound.As the concrete example of surface treating agent used in aforementioned surfaces processing, following (a)~(j) can be enumerated.
(a) higher fatty acids such as stearic acid, oleic acid, erucic acid, palmitinic acid, lauric acid.
(b) metal salts such as the lithium salts of aforementioned (a), sodium salt, sylvite.
(c) sulfuric acid of the higher alcohols such as stearyl alcohol, oleyl alcohol, the sulfuric acid of polyglycol ether, amide linkage sulfuric ester The yin such as salt, ether linking sulfonate, ester linkage sulphonic acid ester, amide linkage alkylaryl sulfonates, ether linking alkylaryl sulfonates Ionic surface active agent.
(d) as orthophosphoric acid and oleyl alcohol, stearyl alcohol etc. list or diester or their mixture, they acid or The phosphates such as alkali metal salt or amine salt.
(e) vinylethoxysilane, γ-methacryloxypropyl trimethoxy silane, (the 2- methoxy of vinyl three Base oxethyl) silane coupling agents such as silane, gamma-amino propyl trimethoxy silicane.
(f) three isostearoyl base titanate esters of isopropyl, isopropyl three (dioctylphyrophosphoric acid ester) titanate esters, isopropyl 13 The titanium coupling agents such as benzene sulfonamide acyl titanate.
(g) the alkali coupling agent such as acetyl aluminum alkoxide diisopropyl hydrochlorate.
(h) ethanolamines such as monoethanolamine, diethanol amine or triethanolamine.
(i) the normal propyl alcohols amine such as n-propanolamine, two n-propanolamines or three n-propanolamines.
(j) the isopropanols amine such as monoisopropanolamine, diisopropanolamine (DIPA) or triisopropanolamine.
Wherein, preferably ethanolamines such as monoethanolamine, diethanol amine or triethanolamine.
(additive amount of multi-element metal compound)
For the additive amount of multi-element metal compound, relative to 100 weight of polyacrylic acid (salt) water-absorbent resin powder Part be preferably 0.01~5 parts by weight, more preferable 0.01~4.5 parts by weight, further preferred 0.1~4.5 parts by weight, further It is preferred that 0.1~4 parts by weight, particularly preferred 0.15~3.5 parts by weight.
Therefore, the content of the multi-element metal compound in final particulate water-absorbing agent of the invention is advised by above-mentioned It is fixed, but the additive amount of multi-element metal compound is a small amount of relative to water absorbing agent, therefore the content in particulate water-absorbing agent is also real It is 0.01 parts by weight~5 parts by weight in matter.
In order to sufficiently moisture absorption be inhibited to agglomerate by only adding multi-element metal compound, more than preferably 0.1 parts by weight, more It is preferred that more than 0.2 parts by weight.In addition, from the viewpoint of water absorbing properties, below preferably 1 parts by weight, more preferable 0.8 parts by weight Below, further preferably below 0.6 parts by weight, below particularly preferred 0.4 parts by weight.
(the addition mixed method of multi-element metal compound)
The manufacturing method of water absorbing agent of the invention may include multi-element metal compound addition process.Multi-element metal compound Adding process is that multi-element metal compound is added to the process of absorbent resin powder.It is excellent that multi-element metal compound adds process It is selected in after drying process and carries out, more preferably carried out after crushing and classification process.Additionally, it is preferred that before as surface cross-linking process step Process and/or rear process are implemented (to implement surface-crosslinked work in the preceding process of multi-element metal compound addition process and/or rear process Sequence), it is carried out particularly preferably after surface cross-linking process step and (adds multi-element metal compound in surface-crosslinked absorbent resin powder). In addition, the process can carry out repeatedly, carried out after drying process at least once in this case, more preferably in crushing and classification It is carried out after process, the preceding process and/or rear process preferably as surface cross-linking process step are implemented, particularly preferably in surface cross-linking process step After carry out.
It is preferred that by multi-element metal compound and absorbent resin powder dry type mixing of the invention.Pass through dry type mixing, institute The Dust Capacity of obtained water absorbing agent reduces, therefore preferably.The dry type mixing refers to that there is no the multi-element metals for this process Compound and absorbent resin powder absorb or the liquid that keeps other than liquid in the state of mixing.Specifically For, including following manner: by the multi-element metal compound containing hygroscopic moisture, the organic compound for being held in interlayer, and tool There are dry residual component, hygroscopic moisture, aforementioned surfaces crosslinking agent to add the water suction of surface crosslinking agent, solvent added in process etc. Property toner, and then do not mix with not adding liquid.
In order to sufficiently obtain the effect of multi-element metal compound, it is sufficiently mixed after preferably adding.Specific mixing condition root It is suitably provided according to used device, treating capacity etc..Can exemplify for example using sieve lattice mixing machine with revolving speed 300rpm The method for being stirred 30 seconds~1 minute or so；It is small that with revolving speed 60rpm 20 minutes~1 is stirred using paddle agitating device When method etc..In addition water-absorbing resins or while assigning the method mixed while vibration, stirring are added The method of powder.
The water-insoluble metal phosphate of anion and divalent comprising phosphoric acid class or the metal cation of trivalent
In the present invention, particulate water-absorbing agent can contain the metal cation of the anion comprising phosphoric acid class and divalent or trivalent Water-insoluble metal phosphate as hygroscopic fluidity improver.Water-insoluble metal phosphate of the invention, has both water suction The reduction of the water absorbing properties such as the AAP of agent is small, inhibits the function of moisture absorption agglomeration.
Anion of the water-insoluble metal phosphate used in the present invention comprising phosphoric acid class and divalent or the metal of trivalent sun Ion.As the anion of phosphoric acid class, phosphate anion, pyrophosphate ion, tripolyphosphate radical ion, six poly- phosphorus can be enumerated Acid ion, five polyphosphate ions, seven polyphosphate ions, three metaphosphate ions, four metaphosphate ions, hexa metaphosphoric acid Two radical ion of radical ion, dihydrogen phosphate ions and phosphoric acid hydrogen etc..As divalent or the metal cation of trivalent, can enumerate calcium from Son, magnesium ion, strontium ion, barium ions, zinc ion, iron ion, aluminium ion, titanium ion, zirconium ion, hafnium ion, tin ion, cerium from Son, scandium ion, ruthenium ion and lanthanum ion etc..It especially can be calcium ion, aluminium ion, can be calcium ion.As specific The salt of calcium can enumerate one-lime phosphate, calcium monohydrogenphosphate, Dicalcium Phosphate, tricalcium phosphate, hydroxyapatite, calcium pyrophosphate, burnt phosphorus Acid dihydride calcium etc..They also can be used a kind or two or more be applied in combination, and also can be used alone tricalcium phosphate.It needs to illustrate , above-mentioned " water-insoluble " refers to the meltage in 25 DEG C of water 100g less than 1g.
The upper limit of the crystallite diameter of water-insoluble metal phosphate used in the present invention can less than 0.15 μm, can not Foot 0.13 μm, can be less than 0.1 μm.The lower limit of crystallite diameter is not particularly limited, but from addition process when operation Property from the viewpoint of, can for 0.005 μm or more, can be 0.01 μm or more.The bound of the crystallite diameter can be as a result, It is suitably selected in above range, such as 0.005 μm or more can be enumerated and less than 0.15 μm, 0.01 μm or more and less than 0.15 μ M, 0.01 μm or more and less than 0.1 μm etc..
It should be noted that in the present invention, as the water-insoluble metal phosphorus contained in the particulate water-absorbing agent of final thing The crystallite diameter of hydrochlorate can satisfy above range, be added to the water-insoluble metal phosphate before absorbent resin powder Crystallite diameter also can satisfy above range.
It, can be in addition, the control method of the crystallite diameter of above-mentioned water-insoluble metal phosphate is not particularly limited It is applicable in known method.And then commercially available water-insoluble metal phosphate also can be used.
It should be noted that the crystallite diameter of water-insoluble metal phosphate can be by the XRD (X that records in embodiment Ray diffraction determination) measurement.
In addition, the upper limit of the average primary particle diameter of water-insoluble metal phosphate used in the present invention can be less than 2.0 μ M, can less than 1.5 μm, can be less than 1.0 μm.Moisture absorption knot can be further reduced if average primary particle diameter is less than 2.0 μm Block.On the other hand, the lower limit value of average primary particle diameter is not particularly limited, but workability when from addition process Viewpoint considers, can be 0.005 μm or more, can be 0.01 μm or more.The bound of the average primary particle diameter can be as a result, Suitably selected in above range, such as 0.005 μm or more can be enumerated and less than 2.0 μm, 0.01 μm or more and less than 1.5 μm, 0.01 μm or more and less than 1.0 μm etc..
It should be noted that be characterized in that in a mode of the invention, it is added to water before absorbent resin powder not The phosphatic average primary particle diameter of solube metallic is met the above range.
It is preferred relative to 100 parts by weight of absorbent resin powder for the additive amount of aforementioned water-insoluble metal phosphate For more than 0.01~2 parts by weight, more preferable 0.01~1 parts by weight, further preferred 0.01 parts by weight and less than 1 parts by weight, spy Not preferably 0.05~0.7 parts by weight, most preferably 0.08~0.6 parts by weight.It is then adequately inhaled if more than 0.01 parts by weight Wet agglomeration performance, if can then maintain sufficient water absorbing properties below 2 parts by weight.Although in addition, being obtained if more than 2 parts by weight To sufficient moisture absorption agglomeration performance, but additive amount increases part and increases as cost, therefore not preferably.
(mixed method of water-insoluble metal phosphate)
Water-insoluble metal phosphate addition process carries out after aforementioned drying process.More preferably in aforementioned crushing and classification It is carried out after process, the preceding process and/or rear process preferably as aforementioned surfaces cross-linking process step are implemented, particularly preferably in aforementioned surfaces It is carried out after cross-linking process step.In addition, the process can carry out repeatedly, it is in this case laggard in aforementioned drying process at least once Row more preferably carries out after aforementioned crushing and classification process, preferably as the preceding process and/or rear work of aforementioned surfaces cross-linking process step Sequence is implemented, is particularly preferably carried out after aforementioned surfaces cross-linking process step.
Water-insoluble metal phosphate of the invention can be added to the state of aqueous slurry solution absorbent resin powder, It can also directly be added with powder shaped, it is preferred that with absorbent resin powder dry type mixing obtained in aforementioned drying process. The dry type mixing refer to there is no for this process water-insoluble metal phosphate and absorbent resin powder absorb or The mixing in the state of liquid other than the liquid of holding.Specifically, including following manner: by water-insoluble gold Belong to phosphate, and surface-crosslinked with adding in dry residual component, hygroscopic moisture, aforementioned surfaces crosslinking agent addition process The absorbent resin powder of agent, solvent etc., and then do not mix with not adding liquid.
In order to sufficiently obtain effect of the invention, water-insoluble metal phosphate is added preferably in absorbent resin powder It is sufficiently mixed later.Specific mixing condition is suitably provided according to used device, treating capacity etc..It can exemplify for example Using sieve the method that lattice mixing machine is stirred 30 seconds~1 minute or so with revolving speed 300rpm；Using paddle agitating device with Revolving speed 60rpm is stirred 20 minutes~1 hour method etc..In addition or while stirring water-absorbing resins powder is added The method at end.
As the device for mixing water-absorbing resins and water-insoluble metal phosphate, such as cylinder type mixing can be enumerated Machine, screw type mixer, screwe-type xtruder, Turbulizer, promise tower mixing machine, V-Mixer, ribbon type mixers, Dual-arm kneader, flow-type mixing machine, airflow mixing machine, rotary disk type mixing machine, roll mixer (roll Mixer), rotary type mixing machine, sieve ground lattice mixing machine etc..As mixed method, in intermittent, continous way, a combination thereof use Any one can be used.From the viewpoint of industrial production, more preferably continuous mixing.
Mixing condition is preferably the degree that absorbent resin powder is not damaged.Such as stirring as mixed device The revolving speed for mixing portion, in the range of being preferably in 1~3000rpm, more preferable 2~500rpm, further preferred 5~300rpm.If It is then not likely to produce the dusting of absorbent resin powder for 3000rpm or less, can prevent water absorption character from reducing.In addition if 1rpm It can then be sufficiently mixed above, obtain reduction (hygroscopic fluidity raising) effect of moisture absorption caking capacity well.
In addition, the temperature of the water-absorbing resins for this process be preferably room temperature~200 DEG C, it is 50~200 DEG C more preferable, into Preferably 50~100 DEG C of one step.
Incorporation time is preferably 1 second~20 minutes, 10 seconds~10 minutes more preferable, 20 seconds~5 minutes further preferred.If Incorporation time is that can then inhibit within 20 minutes or less the dusting of water-absorbing resins.
As a result, as the most preferably absorbent resin powder of the mixing condition for obtaining particulate water-absorbing agent of the invention 50~100 DEG C of temperature, 5~300rpm of revolving speed of mixing part, incorporation time 20 seconds~5 minutes.The mixing obtained under the conditions of this The problems such as particulate water-absorbing agent afterwards, treatability is excellent, will not cause attachment, aggregation, thus can also be not provided with so that it is dry Drying process.By drying appropriate, it is specified that the water of amount (such as water of above-mentioned additive amount) remains on particulate water-absorbing agent, thus may be used To form the particulate water-absorbing agent that electrification is suppressed and impact resistance (abrasion performance) is excellent.
In the present invention, 2 containing divalent and trivalent kind metal cation with hydrotalcite structure and hydroxyl can be used The water-insoluble metal tripolyphosphate of multi-element metal compound and anion and divalent comprising phosphoric acid class or the metal cation of trivalent Both salt.Additive can add together or separately there are in the case where a variety of.In the case where adding respectively, such as can be with Separate 10 seconds, 30 seconds, 1 minute, 3 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 60 Minute, 90 minutes, 120 minutes or more intervals carry out.
In the case where using multi-element metal compound and water-insoluble metal phosphate the two, relative to particulate water-absorbing 100 parts by weight of agent or water-absorbing resins, amount to addition 0.01~1.0 parts by weight, preferably 0.02~0.7 parts by weight, further it is excellent Select 0.03~0.5 parts by weight.
In one scheme, a kind of absorber is provided, contains above-mentioned particulate water-absorbing agent.Above-mentioned absorber do not provide due to Foreign body sensation caused by color, the gel collapse, pachylosis caused by body fluid such as urine, chafing, stench removal energy The problems such as power reduction, chafing, urine leakage, is inhibited.
In one scheme, the present invention provides a kind of hygienic article, contains above-mentioned absorber.Above-mentioned hygienic article (such as paper Diaper), the foreign body sensation caused by not providing coloring, gel collapse, pachylosis, skin caused by the body fluid such as urine The problems such as inflammation, the removal ability reduction of stench, chafing, urine leakage, is inhibited.
In one scheme, the present invention can provide cannot reach in the past have both high water absorption multiplying power and high water absorption speed, have The particulate water-absorbing agent that agglomeration under super-humid conditions inhibits.
In one scheme, the present invention can provide cannot reach in the past have both high water absorption multiplying power and high water absorption speed, have The particulate water-absorbing agent of high absorbent rate under pressure.
In one scheme, the present invention can provide cannot reach in the past have both high water absorption multiplying power and high water absorption speed, have The particulate water-absorbing agent that agglomeration under high absorbent rate under pressure and super-humid conditions inhibits.
The manufacturing method of (4-3) particulate water-absorbing agent
For the general manufacturing process of particulate water-absorbing agent of the invention, in above-mentioned [2] polyacrylic acid (salt) system Explanation in process (2-1)~(2-9) of the manufacturing method of particulate water absorbent containing.
In one scheme, the present invention provides a kind of manufacturing method of particulate water-absorbing agent, which is characterized in that for following (1)~(3) feature gel apply (apply) meet in following (4)~(5) at least one of energy carry out gel powder It is broken,
(1) at least the size on 1 side be average 3000 μm or more, 5000 μm or more, 10mm or more, 30mm or more, 10cm with Upper, 50cm or more, 100cm or more.
(2) gel C RC be 33.0g/g or more, 34.0g/g or more, 35.0g/g or more, 36.0g/g or more, 37.0g/g with Upper, 38.0g/g or more, 39.0g/g or more, 40.0g/g or more.The upper limit of gel C RC is 45.0g/g.
(3) 50 weight % of moisture content or more, 51 weight % or more, 52 weight % or more, 53 weight % or more, 54 weight % Above, 55 weight % or more, 56 weight %, 57 weight %, 58 weight %, 59 weight %, 60 weight % or more, 61 weight %, 62 weight %, 63 weight %, 64 weight %, 65 weight %, 66 weight %, 67 weight %, 68 weight %, 69 weight %, 70 weights Measure % or more, 90 weight % or less.
(4) as gel size reduction energy (GGE) be 29~60, preferably 29~55, more preferable 29~50J/g, be in addition 34 ~60, preferably 34~55, more preferable 34~50J/g
(5) be 15~40 as gel size reduction energy (2) (GGE (2)), preferably 15~38, it is more preferable 15~35J/g, another It is outside 19~40, preferably 19~38, more preferable 19~35J/g.
Here, 1 side of gel refers to taking, the distance between the 2 points maximum length on the surface of gel at any 2 points (so-called major diameter).
Gel C RC
The CRC (gel C RC) of aqueous gel before gel crushing is preferably 33g/g or more.Above-mentioned gel C RC is less than 10 [g/g] or more than 45 [g/g] in the case where, it is difficult to control gel crush when grain shape, size distribution, therefore not preferably. The suitable controls such as crosslinking agent additive amount, other polymerization concentrations when this gel C RC can pass through polymerization.It should be noted that It is preferred that particulate water-absorbing agent or water-absorbing resins with high CRC are the known facts, but found in the present invention, above-mentioned gel In the case that CRC is more than 45 [g/g], it is difficult to control grain shape, size distribution.
Gel size reduction energy (GGE)
It is excellent as upper limit value for aqueous gel to be carried out to the gel size reduction energy (GGE) of gel crushing in the present invention Be selected as 60 [J/g] below, more preferably 50 [J/g] below, further preferably 40 [J/g] below.In addition, as lower limit value, preferably For 15 [J/g] or more, more preferable 17 [J/g] or more, further preferred 20 [J/g] or more, even more preferably 23 [J/g] with Upper, even more preferably 25 [J/g] or more, even more preferably 29 [J/g] or more, most preferably 34 [J/g].For example, of the invention In, for by aqueous gel carry out gel crushing gel size reduction energy (GGE) be 18~60 [J/kg], 20~60 [J/kg], 20~55 [J/g], 20~50 [J/g], 25~50 [J/kg], 25~40 [J/g].By the way that the GGE is controlled in above range, Gel crushing is carried out while shearing compressing force appropriate can be provided for aqueous gel.It should be noted that above-mentioned solidifying Rubber pulverizing energy (GGE) provides including the energy when dry run of gel pulverizer.
The gel size reduction energy (2) except energy when alternatively, it is also possible to by by the dry run of gel pulverizer is (also referred to as For net (net) gel size reduction energy) regulation.That is, the gel for aqueous gel to be carried out to gel crushing crushes energy in the present invention Measure (2) (GGE (2)), as upper limit value, preferably 40 [J/g] below, more preferably 38 [J/g] below, further preferably 35 [J/ G] below.In addition, as lower limit value, preferably 9 [J/g] or more, more preferable 12 [J/g] or more, further preferred 15 [J/g] with Upper, further preferred 15 [J/g] or more, further preferred 19 [J/g] or more.For example, in the present invention, for by aqueous gel into The gel size reduction energy (2) (GGE (2)) that row gel crushes is 9~40 [J/g], 12~38 [J/g] or 15~35 [J/g].It is logical It crosses and the GGE is controlled in above range, coagulated while shearing compressing force appropriate being provided for aqueous gel Rubber pulverizing.
Moisture content
The moisture content of aqueous gel of the invention is 50 weight % or more, 52 weight % or more.By increasing for gel Amount of moisture in the aqueous gel of crushing, the particulate water-absorbing agent of available excellent physical property.The measurement of moisture content can pass through The method recorded in the part of embodiment carries out.
For high CRC (gel C RC is 33g/g or more) gel with high gel size reduction energy (GGE is 18J/g or more) into Row crushes the manufacturing method of not previous particulate water-absorbing agent.In the present invention, the crushing (gel powder of the aqueous gel after polymerization It is broken) in size reduction energy be greater than previous, physically not chemically control the grain shape of particulate water-absorbing agent particle, thus, it is possible to Enough accelerate absorption speed.High water absorption multiplying power and high water absorption speed, the in turn amount of bleeding back and previous particle are had both it is possible thereby to manufacture Shape water absorbing agent compares the particulate water-absorbing agent reduced.
In addition, in the manufacturing method of previous water absorbing agent, (since the crosslinking of gel is close for gel C RC33 or more Degree reduces, becomes soft), it is difficult to grain shape, granularity point are controlled by carrying out gel crushing with high gel size reduction energy Cloth, further investigation as a result, it has been found that, by improving moisture content (reduce solid component), the reduction intensity of gel, even more The gel of high CRC is also easy to control grain shape, size distribution by gel crushing.
In one preferred embodiment, it is characterized in that,
(a) aforementioned gel is carried out to crush until the weight average particle diameter of obtained gel is 360~1500 μm,
(b) 150~200 DEG C of drying temperature, hot wind wind speed vertical direction (up and down direction) be 0.8~2.5m/s, It is preferred that under conditions of 0.003~0.1m/s, further preferred 0.005~0.06m/s, for the gel of belt drying unit area Weight is 10~50kg/m2The gel carry out drying in 10~60 minutes,
(c) it is surface-treated.
Thus, it is possible to show following specialities: even if (1) absorbing, liquid, being not easy to produce gel agglomeration, (high graininess is inhaled Assemble between aqua particle), (2) swell gel elasticity modulus increases, the water absorbing force under load increases, (3) knot of resistance to moisture absorption Block is good etc..
In one preferred embodiment, including relative to particulate water-absorbing agent or 100 parts by weight of water-absorbing resins addition chelating The process of 0.001~0.2 parts by weight of agent, preferably 0.003~0.1 parts by weight, further preferred 0.005~0.06 parts by weight.This It is since the urine patience of particulate water-absorbing agent can be improved by adding chelating agent in particulate water-absorbing agent.
In one preferred embodiment, aforementioned chelating agent is selected from by iminodiacetic acid, hydroxyethyliminodiacetic acid, secondary Nitrilotriacetic acid, three propionic acid of nitrilo-, ethylenediamine tetra-acetic acid, hydroxyethylenediamine triacetic acid, hexamethylene diamine tetraacethyl, two Asias Ethyl pentaacetic acid (DTPA), triethylenetetraaminehexaacetic acid, anti-form-1,2- diaminocyclohexane tetraacethyl, bis- (2- hydroxyls Ethyl) glycine, diamino-propanol tetraacethyl, ethylenediamine -2- propionic acid, glycoletherdiaminotetraacetic acid, bis- (2- hydroxybenzyls) Ethylenediamine diacetic acid, 3- hydroxyl -2,2- iminodisuccinic acid, iminodisuccinic acid, methylglycine diacetic acid, second two Amine-N, N '-two (methylene phosphinic acids), ethylenediamine tetraacetic (methylene phosphinic acids), nitriloacetic acids-two (methylene phosphinic acids), Nitrilo- oxalic acid-(methylene phosphinic acids), nitriloacetic acids-β-propionic acid-methylene phosphonic acid, (the methylene phosphine of nitrilo- three Acid), cyclohexane diamine four (methylene phosphonic acid), ethylenediamine-N, N '-oxalic acid-N, N '-two (methylene phosphonic acid), ethylenediamine-N, N '-two (methylene phosphonic acid), polymethylene diamines four (methylene phosphonic acid), diethylene triamine penta(methylene phosphonic acid) and 1- hydroxyl In the group of base ethidine di 2 ethylhexyl phosphonic acid composition.Wherein, preferably amino carboxylic acid (salt), particularly preferred diethylene-triamine pentaacetic acid (DTPA) (salt).This is because, particulate water-absorbing agent can be improved by adding above-mentioned chelating agent in particulate water-absorbing agent Urine patience.
It further include being inhaled relative to particulate water-absorbing agent or the addition of 100 parts by weight of water-absorbing resins in one preferred embodiment Wet 0.01~1.0 parts by weight of flow improver, preferably 0.02~0.7 parts by weight, further preferred 0.03~0.5 parts by weight Process.By meeting above-mentioned condition, the hygroscopic fluidity of particulate water-absorbing agent is improved, and uses particulate water-absorbing agent and fiber When substrate makes absorber, it is possible to reduce the attachment to appliance arrangement.
In one preferred embodiment, aforementioned hygroscopic fluidity improver is selected from by silica, hydrotalcite, phosphate and aluminium In the group of salt composition.In the present invention, 2 containing divalent and trivalent kind metal cation and hydroxyl with hydrotalcite structure can be enumerated The multi-element metal compound and anion and divalent comprising phosphoric acid class of base or the water-insoluble metal of the metal cation of trivalent Phosphate.By adding above-mentioned hygroscopic fluidity improver, the hygroscopic fluidity of particulate water-absorbing agent is improved, and uses particle When shape water absorbing agent and fiber base material production absorber, it is possible to reduce the attachment to appliance arrangement.
Recycle comminution ratio
When recycling comminution ratio less than 1.10, the logical fluidity (such as SFC) of particulate water-absorbing agent is deteriorated, the micro mist after damage It is significantly increased, so not preferably.Micro mist increase after damage is provided by the measuring method of embodiment, but even if just manufacture Micro mist (example after particulate water absorbent containing；150 μm of JIS standard screen pass through object) less, also due to manufacture diaper when process-induced damage Micro mist is generated, diaper brings the adverse effects such as logical fluidity reduction in actual use, therefore not preferably.
In the present invention, from the viewpoint of traumatic resistance and physical property, circulation comminution ratio be 1.10 or more, preferably 1.15 with Above, more preferable 1.20 or more, further preferred 1.30 or more, particularly preferred 1.35 or more, most preferably 1.40 or more.In addition, from From the viewpoint of absorption speed (such as FSR), recycle comminution ratio the upper limit be 1.50 or less, preferably 1.40 or less, more preferably 1.35 or less, further preferred 1.30 or less, even more preferably 1.25 or less, even more preferably 1.20 or less, especially excellent Select 1.15 or less.
By meeting above-mentioned condition, the absorption speed (such as DRC5 minutes) of particulate water-absorbing agent is improved, due to urine Process-induced damage when cloth manufactures and the micro mist that generates also is greatly decreased, therefore preferably.
In 1 scheme of the invention, a kind of method is provided, being includes gathering for the monomer solution containing acrylic acid (salt) Water absorbing agent that close process, drying process and surface cross-linking process step, that centrifugal separator holding capacity (CRC) is 30g/g or more Manufacturing method includes the process for adding alpha-hydroxy carboxylic acid compounds (salt) before the drying process.While not wishing to be bound by theory, but It is this is because, passing through the addition Alpha-hydroxy carboxylic before drying process in the manufacture of the absorbent with high water absorbent rate The molecular weight of sour (salt), the soluble ingredient in polymer generated reduces, point of imbibition and the soluble ingredient that while being swollen dissolves out Son amount reduces, and thus viscosity reduces, as a result, the sticky feeling, unplessantness displeasure when being used as hygienic material are mitigated.
Added before aforementioned drying process any additive sometimes referred to as in add, after aforementioned drying process addition appoint Meaning additive is sometimes referred to as outer to be added.In the manufacture of the absorbent with high water absorbent rate, add alpha-hydroxy carboxylic acid compounds by interior (salt), the molecular weight of the soluble ingredient dissolved out when can reduce water absorbing agent imbibition and be swollen, as a result, can reduce causes paper to be urinated The sticky feeling of the unplessantness displeasure in actual use such as cloth.
It in water absorbing agent of the invention, from tone (preventing from colouring), prevents the viewpoints such as deterioration from considering, arbitrary chela can be added in addition Mixture (such as diethylene-triamine pentaacetic acid (DTPA) or ethylenediaminetetrakis (methylenephosphonic acid) (EDTMP) etc.).In turn, of the invention Water absorbing agent in, can within add alpha-hydroxy carboxylic acid compounds (salt), from tone (preventing from colouring), prevent deterioration etc. viewpoints consider, add outside appoint Chelating agent (such as diethylene-triamine pentaacetic acid (DTPA) or its salt or the ethylenediaminetetrakis (methylenephosphonic acid) (EDTMP) of meaning Or its salt etc.).
In one preferred embodiment, aforementioned alpha-hydroxy carboxylic acid compounds (salt) are added before, during or after aforementioned polymeric process. More preferable aforementioned alpha-hydroxy carboxylic acid compounds (salt) are added before or during aforementioned polymeric process.Specifically, it is preferable that by aforementioned α-hydroxyl Yl carboxylic acid (salt) is added to the monomer solution before polymerization.Or aforementioned alpha-hydroxy carboxylic acid compounds (salt) are preferably added to polymerization and are caused Monomer solution afterwards is specifically added to the monomer solution after polymerization causes 2 minutes.Aforementioned alpha-hydroxy carboxylic acid compounds (salt) can With from polymerization cause after until the polymerization of monomer solution terminates until any time point (such as polymerize initiation 1 minute after, 2 After minute, after 3 minutes, after five minutes, after ten minutes or after twenty minutes etc.) addition.
In addition in preferred embodiment, preceding method also wraps after aforementioned polymeric process and before aforementioned drying process Gel pulverizing process is included, aforementioned alpha-hydroxy carboxylic acid compounds (salt) are added before or during aforementioned gel pulverizing process.It is more preferably aforementioned Alpha-hydroxy carboxylic acid compounds (salt) add during aforementioned gel pulverizing process.Specifically, aforementioned alpha-hydroxy carboxylic acid compounds (salt) are after polymerisation The addition when gel of obtained aqueous gel crushes.
In addition in preferred embodiment, aforementioned alpha-hydroxy carboxylic acid compounds (salt) are added before or during aforementioned polymeric process.
The bibliography such as scientific literature, patent, the patent application quoted in this specification, by its all with it is respectively specific The identical degree of record be used as with reference to introduce in this specification.
Above for being readily appreciated that preferred embodiment is shown, the present invention is illustrated.Below based on embodiment pair It is illustrated in the present invention, but above-mentioned explanation and embodiment below are not intended to limit merely to illustrate and provide Determine the present invention and provides.Therefore the scope of the present invention is not limited by the embodiment or embodiment specifically recorded in this specification It is fixed, and only limited by patent claims.
Embodiment
The present invention is more particularly described according to embodiment comparative example below, but the present invention is not limited by them It is fixed to explain, by technological means disclosed in each embodiment it is appropriately combined obtained from embodiment be also contained in the scope of the present invention It is interior.
It should be noted that electrical equipment used in embodiment and comparative example (also includes the physical property of particulate water-absorbing agent Measurement), the power supply of 200V or 100V are then used as long as no special note.In addition, particulate water-absorbing agent of the invention is various Physical property then measures under conditions of room temperature (20~25 DEG C), relative humidity 50%RH as long as no special note.
[physical property measurement of particulate water-absorbing agent or water-absorbing resins]
(a) centrifugal separator keeps capacity (CRC)
The centrifugal separator of particulate water-absorbing agent or water-absorbing resins of the invention keeps capacity (lower water suction times of not pressurizeing Rate, CRC) it is measured according to EDANA method (ERT441.2-02).
(b) it pressurizes lower water absorbent rate (AAP)
Water absorbent rate (AAP) is according to EDANA method under the pressurization of particulate water-absorbing agent or water-absorbing resins of the invention (ERT442.2-02) it measures.
(d) moisture content
The moisture content of particulate water-absorbing agent or water-absorbing resins of the invention is measured according to EDANA method (ERT430.2-02). It should be noted that sample size is changed to 1.0g in the present invention, drying temperature is changed to 180 DEG C to measure.
In addition, in the case where the more aqueous gel of amount of moisture (20 weight % of moisture content or more), drying time change It was measured for 24 hours.
(e) saline flow conductivity (SFC)
The saline flow conductivity (SFC) of particulate water-absorbing agent or water-absorbing resins of the invention is according to U.S. Patent No. The measurement of measuring method disclosed in No. 5669894.
(f) dipping keeps 5 score value of capacity: Dunk Retention Capacity (DRC5 minutes)
Using device shown in FIG. 1, in the stainless steel 400 of the bottom weld of the supporting cylinder 100 of the plastics of internal diameter 60mm Purpose wire mesh 101 (38 μm of the size of mesh), it is online at this under conditions of room temperature (20~25 DEG C), humidity 50RH% 1.000 ± 0.005g of uniformly distributed particulate water-absorbing agent or water-absorbing resins measures the weight Wa of measurement device the whole series (g)。
In floor space 400cm2Circle or square Petri dish 103 inside place diameter 120mm glass Glass filter 104 (Sogo Corporation's Physicochemical nitre production society of institute system, pore diameter: 100~120 μm), is added 0.90 weight % salt water 106 (23 ± 0.5 DEG C) are measured to form the upper surface phase same level with glass filter (in the periphery of glass filter On, what 50% or so of liquid surface of slightly floating state or glass filter due to surface tension was covered with the liquid State).On it load diameter 110mm filter paper 105 (ADVANTEC Toyo Co., Ltd., the name of an article: (JIS P 3801, No.2), thickness 0.26mm, retain 5 μm of partial size) 1, soak whole filter paper.
Said determination device the whole series are placed on the filter paper of foregoing wet, it is made to absorb liquid (fluid temperature in measurement It is 23 ± 0.5 DEG C by tight management).After tight management 5 minutes (300 seconds), measurement device the whole series are picked up, its quality Wb is measured (g).Then DRC5 minutes (g/g) is calculated according to following formulas by Wa, Wb.
DRC5 minutes [g/g]={ (Wb-Wa)/(weight of particulate water-absorbing agent or water-absorbing resins) }
(g) surface tension
Into the beaker by the 100ml sufficiently washed, addition is adjusted to 20 DEG C of physiological saline 50ml, uses table first The surface tension of face tensometer (the K11 automatic surface tensometer of KRUSS corporation) measurement physiological saline.In the measurement, surface The value of tension necessarily is in the range of 71~75 [mN/m].
Then, it puts into the beaker of the physiological saline containing adjustment after 20 DEG C of surface tension test by sufficiently washing The fluororesin rotor and particulate water-absorbing agent or water-absorbing resins 0.5g for the 25mm length washed, are stirred under conditions of 500rpm 4 minutes.Stop stirring after 4 points, after aqueous particulate water-absorbing agent or water-absorbing resins sedimentation, is similarly operated again Measure the surface tension of supernatant.It should be noted that in the present invention, using the plate method for using platinum sheet, for plate in each measurement It is preceding sufficiently to be washed with deionized water, and heating washing is carried out with gas burner to use.
(h) size distribution (PSD, σ ζ)
The size distribution (PSD) of particulate water-absorbing agent of the invention and the logstandard deviation (σ ζ) of size distribution are according to beauty The measurement of measuring method disclosed in state's patent application publication the 2006/204755th.
That is, using have 850 μm of aperture, 710 μm, 600 μm, 500 μm, 425 μm, 300 μm, 212 μm, 150 μm, 106 μm, 75 μm of JIS standard screen (The IIDA TESTING SIEVE: internal diameter 80mm；JIS Z8801-1 (2000)) or be equivalent to Particulate water-absorbing agent 10.00g is classified by the sieve of JIS standard screen.After classification, the weight of each sieve is measured, calculates partial size less than 150 μ The weight percent (weight %) of m.It should be noted that " weight percent of the partial size less than 150 μm " refers to passing through aperture Weight rate (%) of the particle of 150 μm of JIS standard screen relative to whole water absorbing agents.
In addition, the retained percentage R of above-mentioned each granularity is drawn on logarithmic probability paper for weight average particle diameter (D50), Weight average particle diameter (D50) is read as by the partial size that the figure will be equivalent to R=50 weight %.It should be noted that weight average particle diameter (D50) Refer to the partial size for corresponding to 50 weight % of whole particulate water-absorbing agents.In addition, the logstandard deviation (σ ζ) of size distribution It is indicated with following formula, the value of σ ζ is smaller, means that size distribution is narrower.
ζ=0.5 σ × ln (X2/X1) (partial size when partial size, X2 when X1 is R=84.1% are 15.9%)
(i) hygroscopic fluidity (Hygroscopic blocking ratio) (B.R.；Blocking Ratio)
After particulate water-absorbing agent or water-absorbing resins 2g are homogenously dispersed the aluminium cup of diameter 52mm, 25 DEG C of temperature, Constant temperature and humidity machine (the PLATINOUSLUCIFERPL-2G of 90 ± 5%RH of relative humidity；Tabai Espec Corp. system) in it is quiet It sets 1 hour.After 1 hour, the particulate water-absorbing agent or water-absorbing resins for being urged into above-mentioned aluminium cup are smoothly transferred to hole On the JIS standard screen (The IIDA TESTING SIEVE: internal diameter 80mm) of 2000 μm of diameter (8.6 mesh of JIS), rotation hammer is used Hitting formula vibrating sieving machine, (Co., Ltd.'s meal field makes made, ES-65 type vibrating sieving machine；Revolving speed 230rpm, number of strokes 130rpm), in room temperature It is classified 5 seconds under conditions of (20~25 DEG C), relative humidity 50%RH.Measurement remains on the graininess on above-mentioned JIS standard screen and inhales The weight (W1 [g]) of aqua or water-absorbing resins and pass through the particulate water-absorbing agent of the JIS standard screen or the weight of water-absorbing resins It measures (W2 [g]), calculates hygroscopic fluidity (Hygroscopic blocking ratio) according to the following formula.It should be noted that the value of caking rate the low, inhale Wet mobility is more excellent.
Hygroscopic fluidity (B.R.) [weight %]={ W1/ (W1+W2) } × 100
(j) soluble ingredient is deteriorated
Contain that is, being measured in the plastic containers with inner cover and outer cover for the capacity 250ml for being incorporated with the rotor of length 35mm Have 0.90 mass % of 0.05 mass % of L-AA and sodium chloride aqueous solution (deterioration test liquid/L-AA 0.10g and The mixture of 0.90 mass % sodium-chloride water solution 199.90g) 200.0g, then by particulate water-absorbing agent or water-absorbing resins 1.00g is added to above-mentioned aqueous solution, is covered tightly with inner cover, outer cover.Then 2 hours are stood in the thermostat for being adjusted to 60 ± 2 DEG C.Through After spending 2 hours, said vesse is taken out by thermostat, stirs 1 hour (revolving speed 500rpm) using blender at room temperature.By above-mentioned Operation extracts the water soluble ingredient of particulate water-absorbing agent or water-absorbing resins.
After stirring, for the extract liquor as above-mentioned aqueous solution, filter paper (ADVANTEC Toyo Co., Ltd. system is used；Product Name: JISP3801No.2/ thickness 0.26mm, retain 5 μm of partial size) 1 be filtered, obtained filtrate 50.0g is as measurement Use liquid.Then, water-soluble with 0.1N-HCl after being titrated until pH 10 for said determination liquid with 0.1N-NaOH aqueous solution Drop is fixed until pH 2.7.Titer at this time is found out as [NaOH] ml and [HCl] ml.
In addition, not adding particulate water-absorbing agent or water-absorbing resins and deterioration test liquid 200.0g being used only, carry out same Operation, find out sky titer ([b2NaOH] ml and [b2HCl] ml).
Calculate deterioration soluble ingredient according to the following formula by above-mentioned titer and average monomer molecular weight.
Deterioration=0.1 × average monomer molecular weight × 200 × 100 soluble ingredient [quality %] × ([HCl]-[b2HCl])/ 1000/1.0/50.0
It should be noted that in the case that average monomer molecular weight is unknown, it is following using utilizing
Neutralization ratio [mole %]={ 1- ([NaOH]-[b1NaOH])/([HCl]-[b1HCl]) } × 100
The neutralization ratio of calculating calculates average monomer molecular weight.
(k) amount of bleeding back
Several method known to the measurement for the amount of bleeding back, following measuring method is its 1, without being limited thereto.
The amount of bleeding back of the absorber of particulate water-absorbing agent of the invention has been used to measure by following steps.
In the rectangle of internal diameter 7.1cm × 8.1cm and the resin pallet of depth 3cm (as material, does not limit especially It is fixed that it is preferable to use ABS resin, acrylic resin, polypropylene, teflon (registered trademark) resins etc.) in equably dissipate Cloth particulate water-absorbing agent 0.900g, on it by top mounting 7cm × 8cm's in a manner of the movement of not particulate water-absorbing agent (by Unicharm Corporation system, trade name MamyPoko banding pattern, L dimension, (in June, 2014 is purchased oneself for use on surface layer Enter, pack the number of bottom surface: 404088043) surface layer taken out, but not limited to this).As model absorber, carry out The measurement of the amount of bleeding back when water suction.
It is slowly put into (in such a way that particulate water-absorbing agent will not be flowed because of liquid) by the central portion of above-mentioned absorber 0.9 weight % sodium-chloride water solution 32ml (wherein, being dropped within 10 seconds terminates).It will be surveyed in advance after five minutes by investment Filter paper (ADVANTEC corporation, model No.2, the size that the filter paper of 100 × 100mm is cut into 7cm × 8cm of weight are determined Into) 20 be placed in absorber, and then the weight by loading identical size (bottom surface with 7cm × 8cm) thereon (1200g).Weight and filter paper are unloaded after 10 seconds, measures the weight of filter paper, thus the weight before subtracting measurement finds out and inhaled by filter paper The liquid measure (g) of receipts.Using the liquid measure as the amount of bleeding back (g).
(l) apparent density
The moisture of water absorbing agent is further removed, the apparent density of (also allowing for the closed pore bubble inside powder) powder passes through Dry type density measurement (the dry type measurement when absorbent resin powder volume of predetermined weight) carries out.
That is, water absorbing agent 6.0g is measured the aluminium cup to the diameter 5cm of bottom surface, it is small that 3 are stood in 180 DEG C of calm drying machine When more than, it is sufficiently dry to 1% or less moisture content.For the water absorbing agent 5.00g after drying, Shimadzu Scisakusho Ltd is utilized Dry type automatic densitometer processed；Micromeritics Auto Pycnometer1320 measures apparent density (weight using helium G/ volume cm3).Replication is until measure same measured value continuous 2 times or more.
(m) real density
For passing through Crushing of Ultrafine to degree, the closed pore bubble destruction by inside or the continuous gas for passing through 45 μm of JIS standard screen The water absorbing agent of alveolation, measures its dry type density, thus finds out the real density in the present invention.
The bubble diameter (closed pore bubble) contained in the inside of water absorbing agent is usually 1~300 μm.But when crushing, approach The part of bubble is preferentially crushed, and does not contain closed pore bubble substantially being crushed to 45 μm of water absorbing agents below, therefore pass through survey The fixed real density by Crushing of Ultrafine to the dry type density of 45 μm of water absorbing agents below, as water absorbing agent.
Real density is measured using water absorbing agent of the JIS standard screen less than 45 μm is crushed to.That is, in ball mill kettle (Teraoka Seiko Co., Ltd. magnetic ball mill kettle model No.90 inside dimension: diameter 80mm height 75mm, outside dimension: diameter 90mm Height 110mm) in, the cylindric magnetic ball (diameter 13mm, length 13mm) of 400g is added relative to water absorbing agent 15.0g, uses Ball mill was with 60Hz Crushing of Ultrafine 2 hours.As a result, obtaining 70 weight % of water absorbing agent, the above are 45 μm of JIS standard screen to pass through object Water absorbing agent.
For being further classified the obtained absorbent resin powder 6.0g less than 45 μm using 45 μm of JIS standard screen, with The apparent density of above-mentioned (l) measures dry type density similarly at 180 DEG C after drying 3 hours, as alleged in the present invention Real density.
(n) air entrapment rate (alias；Closed pore bubble rate)
Use the apparent density (1 [g/cm of density p of the method measurement by recording in above-mentioned " (l) apparent density "3] and Pass through the real density (2 [g/cm of density p for the method measurement recorded in above-mentioned " (m) real density "3]), it is calculated according to following mathematical expressions The air entrapment rate of water absorbing agent.
Air entrapment rate [%]=(ρ 2- ρ 1)/ρ 2 × 100
(o) bulk density
" Density " (ERT460.2-02): pine (volume) density of water absorbing agent is referred to.It should be noted that the application In, bulk density is measured according to JIS K3362 on the basis of referring to ERT460.2-02.
Using bulk density analyzer (it is made that scientific machine production is held in hiding), measured according to JIS K 3362.It will be in order to eliminate The uneven and water absorbing agent 100.0g that has been sufficiently mixed caused by granularity, after being added to the funnel for closing baffle, fastly Baffle is opened fastly, which falls on the recipient of inner capacities 100ml.It should be noted that recipient measures weight in advance (unit；G) (as weight W9).
After the water absorbing agent swelled by recipient is wiped with glass bar, the weight for having the recipient of water absorbing agent is added in correct measurement Measure (unit；G) bulk density is calculated according to the following formula until 0.1g (as weight W10).
Bulk density (g/cm3)=(W10-W9)/100 ... (formulas)
It should be noted that the temperature for the environment being measured is 24.2 DEG C, relative humidity 43%RH.
(p) the micro mist incrementss (traumatic resistance) of damage front and back
Pass through the micro mist incrementss before and after the damage of particulate water-absorbing agent of the invention as defined in aftermentioned measuring method (150 μm of incrementss by object) are preferably 4 weight % or less, 3.5 weight % or less.When within the above range, There is no the problem of physical property reduction in the actual uses such as diaper manufacture.
<the micro mist incrementss after damage imparting>
Following paint mixer tests is carried out for water absorbing agent, with 150 μm of the JIS standard sieve classification in aperture, measurement examination Testing front and back has the incrementss of particle of 150 μm of partial sizes below.
[paint mixer test]
Paint mixer test (PS-test) refer to diameter 6cm, height 11cm glass container in be added it is straight Bead 10g, the water-absorbing resins 30g of diameter 6mm, and it is installed on paint mixer (Japan's making mechanism makees product No.488), It was vibrated 30 minutes with 800cycle/ minutes (CPM), device is disclosed in detail in Japanese Unexamined Patent Publication 9-235378 bulletin.
After oscillation, bead is removed with the JIS standard screen of aperture 2mm, obtains the water-absorbing resins for imparting damage.
(q) water soluble ingredient (Ext)
The water soluble ingredient (Ext) of particulate water-absorbing agent of the invention is measured according to EDANA method (ERT470.2-02).
(r) surface area
The surface area of particulate water-absorbing agent of the invention can be for the 3 D analysis device (example by the way that X-ray is utilized Such as micro- focusing X-ray CT system inspeXio SMX-225CT or the inspeXio SMX- of Shimadzu Scisakusho Ltd's system The result that 100CT) measures is solved using 3 D analysis software (such as high speed three-dimensional analysis software TRI/3D-VOL-FCS64) Analysis etc. measures.In addition, can also measure above-mentioned air entrapment rate etc. simultaneously.
(s) granulometry of the multi-element metal compound (hydrotalcite) on water absorbing agent
For the granularity of multi-element metal compound (hydrotalcite) of the invention, measurement is attached to water-absorbing resins surface Particle 100 fixed-direction diameters, find out average grain diameter.Measurement device uses 3D real surface viewing microscope (Keyence Corporation system).
Specifically, first using have 600 μm of aperture, 300 μm of JIS standard screen (JIS Z8801-1 (2000)) or Water absorbing agent added with multi-element metal compound is classified by comparable sieve, takes out the water suction of the partial size with 300 μm~600 μm Agent.The water absorbing agent about 0.05g is interspersed among to SEM conductive carbon double faced adhesive tape (Xin EM Co., Ltd. of 0.8cm × 0.8cm System) on, it is pasted on 3D real surface viewing microscope observation pedestal.Then (the detection of 3D real surface viewing microscope is utilized Device；Secondary electron detector, acceleration voltage；1.7kV, multiplying power；5000 times) image on water absorbing agent surface is obtained, measurement is attached to The fixed-direction diameter of the multi-element metal compound on water absorbing agent surface, finds out average grain diameter.(it should be noted that only including hole 300 μm of diameter of sieve by object or only comprising the non-water absorbing agent by object of 600 μm of aperture sieve in the case where, suitably will by close to Particle that the particle for the size distribution that 600~300 μm of aperture is classified with 300 μm of amplitudes of bound, such as 600~900 μm, 300 μ M~0 μm is as substitution to measure).
(t) quantitative approach of the multi-element metal compound (hydrotalcite) of X-ray diffraction is utilized
By using the powder of powder x-ray diffraction device (Rigaku Corporation system, ProductName: SmartLab) Last X-ray diffraction (XRD) carries out the qualitative of the hydrotalcite compound contained in absorbent resin powder and quantifies.It is described below Determination condition.
X-ray source: CuK alpha ray (λ=0.15418nm)/45kV/200mA
Scanning range: 2 θ=5~80 °
Scanning speed: 3 °/minute
The glass system sample holder that sample is filled uniformly with to recess 0.5mm is made by outside using other glass plates The surface for the sample filled is flat.Then, the glass plate that will be filled with sample is set to powder x-ray diffraction device, obtains XRD diagram case.
Whether there is hydrotalcite compound for absorbent resin powder, can by obtained XRD diagram case whether It was found that the peaks of hydrotalcite compound distinctive 2 strong lines determines.Specifically, in 2 angles of diffraction (a) below and (b) In the case where all there is diffraction maximum in position, it is possible to determine that there is hydrotalcite compound.
(a) 2 θ=11.5 ° ± 1.0 °
(b) 2 θ=22.9 ° ± 1.0 °
It should be noted that the diffraction maximum for being present in the position of (a) is determined based on for hydrotalcite compound (003) The diffracted ray in face, the diffraction maximum for being present in the position of (b) are to determine the diffraction based on for hydrotalcite compound (006) face Line.
The hydrotalcite contained in absorbent resin powder can quantitatively be calculated by the diffraction peak intensity of XRD diagram case.Specifically For, the XRD determining of the absorbent resin powder of the hydrotalcite containing known quantity is carried out, by 2 θ=11.5 ° (a) of XRD diagram case ± 1.0 ° or (b) standard curve is made in the diffraction peak intensity of 2 θ=22.9 ° ± 1.0 °.Using the standard curve as external perimysium reference, Find out the hydrotalcite compound content (quality %) of absorbent resin powder.
(u) the crystallite diameter measurement of water-insoluble metal phosphate
By using powder x-ray diffraction device (Spectris Co., Ltd. system, ProductName: X ' Pert PRO MPD powder x-ray diffraction (XRD)) carries out the crystallite diameter measurement of water-insoluble metal phosphate.Measurement strip described below Part.
X-ray source: CuK alpha ray (λ=0.15406nm)/45kV/40mA
Scanning range: 2 θ=20~40 degree
Step-length: 0.017 degree
The step-length time: 50 seconds
The glass system sample holder that sample is filled uniformly with to recess (depth) 0.5mm uses other glass by outside Glass plate keeps the surface of filled sample flat.Then, the glass plate that will be filled with sample is set to powder x-ray diffraction dress It sets, obtains XRD diagram case.
The crystallite diameter of water-insoluble metal phosphate be using the highest diffraction maximum of relative intensity half-peak breadth and by The formula of Debye-Sherrer calculates.
The formula of Deby-Sherrer: d=0.9 × λ ÷ (B × cos θ)
(d: crystallite diameter, λ: X-ray wavelength, B: the half-peak breadth of diffraction maximum, θ: 2 θ of the angle of diffraction/θ)
For the crystallite diameter of the water-insoluble metal phosphate on particulate water-absorbing agent, measurement is added with water-insoluble gold The XRD for belonging to phosphatic particulate water-absorbing agent, finds out crystallite diameter.
Specifically, first using the JIS standard screen (JIS Z8801-1 (2000)) or comparable with 106 μm of aperture Particulate water-absorbing agent added with water-insoluble metal phosphate is classified by sieve, takes out the particle with 106 μm of partial sizes below Shape water absorbing agent 0.5g.Then, XRD is measured by gimmick same as described above, crystallite diameter is calculated by obtained diffraction maximum.
(v) measurement of the average primary particle diameter of water-insoluble metal phosphate
The average primary particle diameter of water-insoluble metal phosphate used in the present invention refers to water-insoluble metal tripolyphosphate The specific surface area equivalent spherical diameter of salt.The specific surface area equivalent spherical diameter, which is referred to, is assumed to ball, by utilizing for the shape of particle The partial size for the specific surface area conversion that BET method is found out, is calculated by following formula.
D={ 6/ (Sg × ρ) }
Here,
D: specific surface area equivalent spherical diameter (μm)
Sg: specific surface area (m2/g)
ρ: the real density (g/cm of particle3)。
The device using nitrogen adsorption BET1 point method measurement the specific area can be used in the measurement of above-mentioned specific surface area, can arrange It enumerates such as Mountech corporation Macsorb HM model-1210.Specific measuring method is as described below.
Firstly, filling measurement sample 0.5g or so (below using sample loading as a (g)) in glass system dedicated slot.It connects The dedicated slot is installed on mensuration machine main body, 110 DEG C are carried out in a nitrogen atmosphere, after 60 minutes dry degassings, by this Dedicated slot is cooled to room temperature.
Then it while the dedicated slot is cooling with liquid nitrogen, is used in the dedicated slot with 25ml/ minutes flow-through assays of flow Gas (mixed gas of 70 volume % of nitrogen (the 1st grade) 30 volume % helium), adsorbance of the measurement measurement gas to sample (V(cm3))。
Measured value obtained in operating above is suitable for following formula, calculates the specific surface area Sg (m of the sample2/g)。
Sg=S/a={ K × (1-P/P0)×V}/a
Here,
S: the total surface area (m of sample2)
K: gas constant (being 4.29 in this measurement)
P/P0: 97% (being 0.29 in this measurement) of the relative pressure of adsorbed gas, mixing ratio.
It should be noted that using the following value in the present invention as real density.
Calcium phosphate: 3.1 (g/cm3)
Aluminum phosphate: 2.6 (g/cm3)
Apatite α-TCP:2.6 (g/cm3)
NOVARON AGZ010:5.1 (g/cm3)
Calcium phosphate TTCP:3.1 (g/cm3)
Aerosil 200CF:2.2 (g/cm3)
(w) measurement of diffusion absorption multiplying power
According to the measuring method recorded in Japanese Unexamined Patent Publication 2010-142808, the diffusion absorption times of particulate water-absorbing agent is carried out The measurement of rate.Specifically as described below.
Measurement device used in measurement while with reference first to Fig. 2 and Fig. 3 below for diffusion absorption multiplying power carries out Simple declaration.
As shown in Fig. 2, measurement device includes container 2, the extraneous gas of balance 1, the specified volume being placed on the balance 1 Suction line 3, conduit 4, glass filter 6 and the determination part 5 being placed on the glass filter 6.Said vesse 2 is at the top of it There is opening portion 2b with opening portion 2a, in its side surface part, 2a is embedded in extraneous gas suction line 3 in opening portion, on the other hand exists Opening portion 2b installs conduit 4.In addition, being packed into the physiological saline 12 of specified amount in container 2.The lower end of extraneous gas suction line 3 It is submerged in physiological saline 12.Above-mentioned glass filter 6 is formed with diameter 70mm.Then, container 2 and glass filter 6 pass through Conduit 4 interconnects.In addition, glass filter 6 keeps the formation of its upper surface slightly higher relative to the lower end of extraneous gas suction line 3 Position fix.
As shown in figure 3, said determination portion 5 has filter paper 7, sheet material 8, supporting cylinder 9, the bottom for being pasted on the supporting cylinder 9 The wire mesh 10 and weight 11 in portion.And determination part 5 successively loads filter paper 7, sheet material 8, bearing circle on glass filter 6 While cylinder 9 (that is wire mesh 10), the mounting weight 11 inside supporting cylinder 9, i.e. on wire mesh 10.Sheet material 8 It is formed by polyethylene terephthalate (PET), in the face of the thickness 0.1mm of opening portion of the central portion with diameter 18mm Packet round is formed.Supporting cylinder 9 is formed with internal diameter 60mm.Wire mesh 10 is formed by stainless steel, according to JIS standard with 400 mesh (38 μm of the size of mesh) is formed.And the particulate water-absorbing agent of specified amount is equably dispensed on wire mesh 10.Weight 11 Its weight is adjusted so as to 20g/cm uniformly applied for wire mesh 10, i.e. particulate water-absorbing agent2(1.96kPa's) is negative Lotus.
Diffusion absorption multiplying power is measured using the measurement device of above structure.It is illustrated below for measuring method.
It carries out that the physiological saline 12 of specified amount is added in container 2 first, be embedded in extraneous gas suction line 3 etc. in container 2 Defined preparation operation.Then filter paper 7 is loaded on glass filter 6, so that its opening portion is located at glass filter 6 sheet material 8 Central part be placed on the filter paper 7.On the other hand, while carrying out these mounting operations, inside supporting cylinder 9, i.e. Particulate water-absorbing agent 1.5g is equably dispensed on wire mesh 10, and weight 11 is loaded on the particulate water-absorbing agent.
Then, particulate water-absorbing agent and the above-mentioned supporting cylinder 9 of weight 11 are placed with by wire mesh 10, that is to be made The center portion thereof is consistent with the central part of glass filter 6 to be placed on sheet material 8.
Then, time point graininess suction by 60 minutes by loading supporting cylinder 9 on sheet material 8 is measured using balance 1 The weight W for the physiological saline 12 that aqua is absorbed2(g).It should be noted that as shown in Figure 3 and Figure 4, physiological saline 12 is logical After crossing the opening portion of sheet material 8, while the transverse direction of particulate water-absorbing agent (in figure, is depicted with arrows) generally uniform diffusion, It is absorbed by particulate water-absorbing agent.
Then by above-mentioned weight W2, according to the following formula
Diffusion absorption multiplying power (g/g)=weight W2(g)/particulate water-absorbing agent weight (g)
It calculates by the diffusion absorption multiplying power (g/g) absorbing after sixty minutes.
In addition, the above-mentioned imbibition time was changed to 10 minutes by 60 minutes, 10 minutes (g/ of diffusion absorption multiplying power are thus calculated G) value.
In Production Example below, as the manufacturing device of polyacrylic acid (salt) water-absorbent resin powder, prepare by polymerizeing Process, gel pulverizing process, drying process, pulverizing process, classification process, surface cross-linking process step, cooling process, whole grain process, The apparatus for continuously production that conveying operation between connection each process is constituted.The production capacity of the apparatus for continuously production is 3500 [kg/hr], above-mentioned operation can be respectively 1 series or 2 series or more.In the case that 2 series are above, production capacity is with each series Total amount indicate.Using the apparatus for continuously production, it is continuously manufactured by polyacrylic acid (salt) water-absorbent resin powder.
[Production Example 1]
Production includes 300 parts by weight of acrylic acid, 48 weight % sodium hydrate aqueous solution, 100 parts by weight, polyethylene glycol dipropyl Olefin(e) acid ester (average n number 9) 0.94 parts by weight, 0.1 3 sodium water solution of weight % 5 acetic acid of diethylenetriamines, 16.4 parts by weight, go from The monomer solution (1) of sub- 314.3 parts by weight of water.
Then, after temperature adjustment to 38 DEG C of above-mentioned monomer solution (1) is continuously supplied using constant displacement pump, so it is continuously online Mix 48 weight % sodium hydrate aqueous solution, 150.6 parts by weight.It should be noted that at this point, water-soluble by heat of neutralization monomer Up to 80 DEG C of the liquid temperature rise of liquid (1).
In turn, continuously after 4 weight % sodium persulfate aqueous solution of on-line mixing, 14.6 parts by weight, form 10mm's with thickness Mode be continuously fed to include the planar condensation zone that both ends have dykes and dams continuous polymerization machine.Then, it continuously carries out It polymerize (polymerization time 3 minutes), obtains band-like aqueous gel (1).By obtained band-like aqueous gel (1) relative to poly- The direction of travel of crossed belt equally spaced continuous cutting-off in a manner of shearing length 300mm in width direction, thus obtains containing water-setting Glue (1).Aqueous gel (1) is CRC 33.5 [g/g], 49.5 weight % of resin solid content.
[Production Example 2]
Production includes 300 parts by weight of acrylic acid, 48 weight % sodium hydrate aqueous solution, 100 parts by weight, polyethylene glycol dipropyl Olefin(e) acid ester (average n number 9) 0.61 parts by weight, are gone at 1.0 5 sodium water solution of weight % ethylenediaminetetrakis (methylenephosphonic acid), 6.5 parts by weight The monomer solution (2) of 346.1 parts by weight of ionized water.
Then, after temperature adjustment to 40 DEG C of above-mentioned monomer solution (2) is continuously supplied using constant displacement pump, so it is continuously online Mix 48 weight % sodium hydrate aqueous solution, 150.6 parts by weight.It should be noted that at this point, water-soluble by heat of neutralization monomer Up to 81 DEG C of the liquid temperature rise of liquid (2).
In turn, continuously after 4 weight % sodium persulfate aqueous solution of on-line mixing, 14.6 parts by weight, form 10mm's with thickness Mode be continuously fed to include the planar condensation zone that both ends have dykes and dams continuous polymerization machine.Then, it continuously carries out It polymerize (polymerization time 3 minutes), obtains band-like aqueous gel (2).By obtained band-like aqueous gel (2) relative to poly- The direction of travel of crossed belt equally spaced continuous cutting-off in a manner of shearing length 300mm in width direction, thus obtains containing water-setting Glue (2).Aqueous gel (2) is CRC 36.0 [g/g], 48.1 weight % of resin solid content.
[Production Example 3]
Production includes 300 parts by weight of acrylic acid, 48 weight % sodium hydrate aqueous solution, 100 parts by weight, polyethylene glycol dipropyl Olefin(e) acid ester (average n number 9) 0.61 parts by weight, 0.1 5 sodium water solution of weight % ethylenediaminetetrakis (methylenephosphonic acid), 16.4 parts by weight, The monomer solution (3) of 274.4 parts by weight of deionized water.
Then, after temperature adjustment to 38 DEG C of above-mentioned monomer solution (3) is continuously supplied using constant displacement pump, so it is continuously online Mix 48 weight % sodium hydrate aqueous solution, 150.6 parts by weight.It should be noted that at this point, water-soluble by heat of neutralization monomer Up to 83 DEG C of the liquid temperature rise of liquid (3).
In turn, continuously after 4 weight % sodium persulfate aqueous solution of on-line mixing, 14.6 parts by weight, form 10mm's with thickness Mode be continuously fed to include the planar condensation zone that both ends have dykes and dams continuous polymerization machine.Then, it continuously carries out It polymerize (polymerization time 3 minutes), obtains band-like aqueous gel (3).By obtained band-like aqueous gel (3) relative to poly- The direction of travel of crossed belt equally spaced continuous cutting-off in a manner of shearing length 300mm in width direction, thus obtains containing water-setting Glue (3).Aqueous gel (3) is CRC 33.6 [g/g], 53.1 weight % of resin solid content.
[Production Example 4]
Production includes 300 parts by weight of acrylic acid, 48 weight % sodium hydrate aqueous solution, 100 parts by weight, polyethylene glycol dipropyl Olefin(e) acid ester (average n number 9) 1.46 parts by weight, 0.1 3 sodium water solution of weight % 5 acetic acid of diethylenetriamines, 16.4 parts by weight, go from The monomer solution (4) of sub- 361 parts by weight of water.
Then, after temperature adjustment to 42 DEG C of above-mentioned monomer solution (4) is continuously supplied using constant displacement pump, so it is continuously online Mix 48 weight % sodium hydrate aqueous solution, 150.6 parts by weight.It should be noted that at this point, water-soluble by heat of neutralization monomer Up to 81 DEG C of the liquid temperature rise of liquid (4).
In turn, continuously after 4 weight % sodium persulfate aqueous solution of on-line mixing, 14.6 parts by weight, form 10mm's with thickness Mode be continuously fed to include the planar condensation zone that both ends have dykes and dams continuous polymerization machine.Then, it continuously carries out It polymerize (polymerization time 3 minutes), obtains band-like aqueous gel (4).By obtained band-like aqueous gel (4) relative to poly- The direction of travel of crossed belt equally spaced continuous cutting-off in a manner of shearing length 300mm in width direction, thus obtains containing water-setting Glue (4).Aqueous gel (4) is CRC 33.3 [g/g], 47.1 weight % of resin solid content.
[Production Example 5]
Production includes 300 parts by weight of acrylic acid, 48 weight % sodium hydrate aqueous solution, 100 parts by weight, polyethylene glycol dipropyl Olefin(e) acid ester (average n number 9) 0.61 parts by weight, are gone at 1.0 5 sodium water solution of weight % ethylenediaminetetrakis (methylenephosphonic acid), 6.5 parts by weight The monomer solution (5) of 371.6 parts by weight of ionized water.
Then, after temperature adjustment to 42 DEG C of above-mentioned monomer solution (5) is continuously supplied using constant displacement pump, so it is continuously online Mix 48 weight % sodium hydrate aqueous solution, 150.6 parts by weight.It should be noted that at this point, water-soluble by heat of neutralization monomer Up to 81 DEG C of the liquid temperature rise of liquid (5).
In turn, continuously after 4 weight % sodium persulfate aqueous solution of on-line mixing, 14.6 parts by weight, form 10mm's with thickness Mode be continuously fed to include the planar condensation zone that both ends have dykes and dams continuous polymerization machine.Then, it continuously carries out It polymerize (polymerization time 3 minutes), obtains band-like aqueous gel (5).By obtained band-like aqueous gel (5) relative to poly- The direction of travel of crossed belt equally spaced continuous cutting-off in a manner of shearing length 300mm in width direction, thus obtains containing water-setting Glue (5).Aqueous gel (5) is CRC 36.7 [g/g], 47.2 weight % of resin solid content.
[Production Example 6]
Production includes 300 parts by weight of acrylic acid, 48 weight % sodium hydrate aqueous solution, 100 parts by weight, polyethylene glycol dipropyl Olefin(e) acid ester (average n number 9) 0.78 parts by weight, 0.1 3 sodium water solution of weight % 5 acetic acid of diethylenetriamines, 16.4 parts by weight, go from Sub- 336.5 parts by weight of water, liquid malic acid (DL-malic acid, 50 weight % aqueous solutions, Fukawa Chemical Industries Co., Ltd.'s system, food Product additive grade) 2.2 parts by weight monomer solution (6).
Then, after temperature adjustment to 38 DEG C of above-mentioned monomer solution (6) is continuously supplied using constant displacement pump, so it is continuously online Mix 48 weight % sodium hydrate aqueous solution, 150.6 parts by weight.It should be noted that at this point, water-soluble by heat of neutralization monomer Up to 83 DEG C of the liquid temperature rise of liquid (6).
In turn, continuously after 4 weight % sodium persulfate aqueous solution of on-line mixing, 14.6 parts by weight, form 10mm's with thickness Mode be continuously fed to include the planar condensation zone that both ends have dykes and dams continuous polymerization machine.Then, it continuously carries out It polymerize (polymerization time 3 minutes), obtains band-like aqueous gel (6).By obtained band-like aqueous gel (6) relative to poly- The direction of travel of crossed belt equally spaced continuous cutting-off in a manner of shearing length 300mm in width direction, thus obtains containing water-setting Glue (6).Aqueous gel (6) is CRC 36.1 [g/g], 48.0 weight % of resin solid content.
[Production Example 7]
Production includes 300 parts by weight of acrylic acid, 48 weight % sodium hydrate aqueous solution, 100 parts by weight, polyethylene glycol dipropyl Olefin(e) acid ester (average n number 9) 0.87 parts by weight, 0.1 3 sodium water solution of weight % 5 acetic acid of diethylenetriamines, 16.4 parts by weight, go from Sub- 360.2 parts by weight of water, DL-malic acid (powder, Fukawa Chemical Industries Co., Ltd.'s system, food additives grade) 1.8 weight The monomer solution (7) of part.
Then, after temperature adjustment to 38 DEG C of above-mentioned monomer solution (7) is continuously supplied using constant displacement pump, so it is continuously online Mix 48 weight % sodium hydrate aqueous solution, 150.6 parts by weight.It should be noted that at this point, water-soluble by heat of neutralization monomer Up to 81 DEG C of the liquid temperature rise of liquid (7).
In turn, continuously after 4 weight % sodium persulfate aqueous solution of on-line mixing, 14.6 parts by weight, form 10mm's with thickness Mode be continuously fed to include the planar condensation zone that both ends have dykes and dams continuous polymerization machine.Then, it continuously carries out It polymerize (polymerization time 3 minutes), obtains band-like aqueous gel (7).By obtained band-like aqueous gel (7) relative to poly- The direction of travel of crossed belt equally spaced continuous cutting-off in a manner of shearing length 300mm in width direction, thus obtains containing water-setting Glue (7).Aqueous gel (7) is CRC 36.8 [g/g], 47.0 weight % of resin solid content.
[Production Example 8]
Production includes 300 parts by weight of acrylic acid, 48 weight % sodium hydrate aqueous solution, 100 parts by weight, polyethylene glycol dipropyl Olefin(e) acid ester (average n number 9) 1.42 parts by weight, 0.1 3 sodium water solution of weight % 5 acetic acid of diethylenetriamines, 16.4 parts by weight, go from The monomer solution (8) of sub- 273.2 parts by weight of water.
Then, after temperature adjustment to 38 DEG C of above-mentioned monomer solution (8) is continuously supplied using constant displacement pump, so it is continuously online Mix 48 weight % sodium hydrate aqueous solution, 150.6 parts by weight.It should be noted that at this point, water-soluble by heat of neutralization monomer Up to 87 DEG C of the liquid temperature rise of liquid (8).
In turn, continuously after 4 weight % sodium persulfate aqueous solution of on-line mixing, 14.6 parts by weight, form 10mm's with thickness Mode be continuously fed to include the planar condensation zone that both ends have dykes and dams continuous polymerization machine.Then, it continuously carries out It polymerize (polymerization time 3 minutes), obtains band-like aqueous gel (8).By obtained band-like aqueous gel (8) relative to poly- The direction of travel of crossed belt equally spaced continuous cutting-off in a manner of shearing length 300mm in width direction, thus obtains containing water-setting Glue (8).Aqueous gel (8) is CRC 32.1 [g/g], 53.2 weight % of resin solid content.
[embodiment 1]
(gel crushing)
Aqueous gel (1) obtained in above-mentioned Production Example 1 is supplied to screw extruder and carries out gel crushing.As the spiral shell Bar extruder has diameter 100mm, aperture 9.5mm, hole count 40, percent opening 36.1%, thickness 10mm using in front end The masticator of the outer diameter 86mm of the screw shaft of porous plate.In the state that the screw shaft revolving speed of the masticator is 130rpm, with 4640 [g/ minutes] supply aqueous gels (1), while with 83 [g/ minutes] supply vapor.Gel size reduction energy at this time It (GGE) be 26.9 [J/g], GGE (2) is 13.6 [J/g].It should be noted that the temperature of the aqueous gel (1) before gel crushing Be 80 DEG C, gel it is smashed crush gel, i.e. graininess aqueous gel (1) temperature be increased to 85 DEG C.
Graininess aqueous gel (1) obtained in above-mentioned gel pulverizing process is 49.1 weight % of resin solid content, again The logstandard deviation (σ ζ) 1.01 of equal 994 μm of partial size (D50), size distribution.The condition of the gel pulverizing process such as 1 institute of table Show, the physical property of graininess aqueous gel (1) it is as shown in table 2.
(drying)
Then above-mentioned graininess aqueous gel (1) is spread on vent board (this within 1 minute after gel crushes When the temperature of graininess aqueous gel (1) be 80 DEG C), carry out drying in 30 minutes at 185 DEG C, obtain dry polymer (1).Heat The mean wind speed of wind relative to zone of aeration direction of travel vertical direction be 1.0 [m/s].It should be noted that the wind of hot wind Speed utilizes Kanomax Japan, Inc. steady temperature hot type airspeedometer Anemomaster 6162 to measure.
(crushing and classification)
Then, dry polymer obtained in above-mentioned drying process (11) total amount is supplied to triple-roller mill and is crushed (powder Broken process), it then and then with the JIS standard screen in 710 μm and 175 μm of aperture is classified, thus obtains unsetting broken shape Water-absorbent besin particles (1).Water-absorbent besin particles (1) are 348 μm of weight average particle diameter (D50), the logarithmic scale of size distribution is inclined Difference (σ ζ) 0.32, CRC 42.1 [g/g], 150 μm pass through particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) 0.5 weight Measure %.
(surface treating additive addition)
It uniformly mixes sequentially for above-mentioned (1) 100 parts by weight of water-absorbent besin particles comprising ethylene glycol diglycidyl base (the covalent bond of 0.025 parts by weight of ether, 3.0 parts by weight of 0.4 parts by weight of 1,4- butanediol, 0.6 parts by weight of propylene glycol and deionized water Conjunction property) surface-crosslinker solution, heats 30 minutes or so at 190 DEG C so that obtained absorbent resin powder (1) CRC be 35g/g.Then cooled down, implement above-mentioned coating mixing machine test, assign be equivalent to manufacturing process damage it Afterwards, 100 parts by weight of water-absorbent besin particles are equably mixed comprising 1 parts by weight of water, 5 acetic acid of diethylenetriamines, 3 sodium The aqueous solution of 0.01 parts by weight.At 60 DEG C after drying 1 hour, by 710 μm of the JIS standard screen in aperture, dioxy is equably added SiClx (trade name: Aerosil 200, Nippon Aerosil Co., Ltd. system) 0.4 parts by weight.So obtain graininess suction Aqua (1).The various physical property of particulate water-absorbing agent (1) are as shown in table 3~6.It should be noted that after paint mixer test 150 μm when further implementing particulate water-absorbing agent paint mixer test by the expression of particle incrementss (assuming that diaper etc. Absorber manufacture when process-induced damage) 150 μm of incrementss by particle.
[embodiment 2]
Operation same as Example 1 is carried out other than operation as shown below.Using obtained in above-mentioned Production Example 2 Aqueous gel (2) substitutes aqueous gel (1).The aperture of the porous plate of the front end of screw extruder is changed to 8mm.At this time Gel size reduction energy (GGE) is 31.9 [J/g], GGE (2) is 17.5 [J/g].It should be noted that aqueous before gel crushing The temperature of gel (2) is 80 DEG C, the temperature of the smashed crushing gel of gel, i.e. graininess aqueous gel (2) is increased to 84 DEG C.
Graininess aqueous gel (2) obtained in above-mentioned gel pulverizing process is 47.5 weight % of resin solid content, again The logstandard deviation (σ ζ) 0.95 of equal 860 μm of partial size (D50), size distribution.The condition of the gel pulverizing process such as 1 institute of table Show, the physical property of graininess aqueous gel (2) it is as shown in table 2.
Then drying and crushing progressive operation same as Example 1 is carried out, the water imbibition of unsetting broken shape is obtained Resin particle (2).Water-absorbent besin particles (2) are the logstandard deviation (σ ζ) of 355 μm of weight average particle diameter (D50), size distribution 0.32, CRC 48.2 [g/g], 150 μm pass through particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) 0.4 weight %.
It uniformly mixes sequentially for above-mentioned (2) 100 parts by weight of water-absorbent besin particles comprising ethylene glycol diglycidyl base (the covalent bond of 0.025 parts by weight of ether, 3.0 parts by weight of 0.4 parts by weight of ethylene carbonate, 0.6 parts by weight of propylene glycol and deionized water Conjunction property) surface-crosslinker solution, heats 30 minutes or so at 190 DEG C so that obtained absorbent resin powder (2) CRC be 38g/g.Then operation similarly to Example 1 is carried out.So obtain particulate water-absorbing agent (2).Particulate water-absorbing agent (2) various physical property are as shown in table 3~6.
[embodiment 3]
Carry out the net in 710 μm of aperture used in alternate embodiment 2 using 850 μm of net, in addition to this carries out and embodiment 2 Identical operation.The obtained water-absorbent besin particles (3) are the logarithmic scale of 431 μm of weight average particle diameter (D50), size distribution Deviation (σ ζ) 0.35, CRC 48.2 [g/g], 150 μm by particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) be 0.3 Weight %.In addition, the various physical property of obtained particulate water-absorbing agent (3) are as shown in table 3~6.
[embodiment 4]
(1) 100 parts by weight of water-absorbent besin particles obtained in embodiment 1 are uniformly mixed comprising 1,4- butanediol (covalently bonded) surface-crosslinker solution of 2.0 parts by weight of 0.3 parts by weight, 0.5 parts by weight of propylene glycol and deionized water, Heat 30 minutes or so at 200 DEG C so that the CRC of obtained absorbent resin powder (4) is 35g/g.Then it carries out cold But, implement the test of above-mentioned coating mixing machine, imparting is equivalent to after the damage of manufacturing process, for water-absorbent besin particles 100 Parts by weight equably mix the aqueous solution comprising 0.5 parts by weight of water, 0.05 parts by weight of polyethylene glycol (average molecular weight 400), into One step is uniformly mixed comprising 5 acetic acid of diethylenetriamines, 3 sodium, 0.01 parts by weight, 27.5 weight % aluminum sulfate aqueous solutions (according to oxygen Change aluminium and be scaled 8 weight %) 0.6 parts by weight, 60 weight % sodium lactate aqueous solution 0.1 parts by weight, 0.02 parts by weight of propylene glycol Aqueous solution.At 60 DEG C after drying 1 hour, pass through 710 μm of the JIS standard screen in aperture.So obtain particulate water-absorbing agent (4).? The various physical property of particulate water absorbent containing (4) are as shown in table 3~6.
[embodiment 5]
(1) 100 parts by weight of water-absorbent besin particles obtained in embodiment 1 are uniformly mixed comprising ethylene carbonate 0.3 parts by weight, 0.5 parts by weight of propylene glycol, 2.0 parts by weight of deionized water, polyoxyethylene (20) sorbitan list are stearic (covalently bonded) surface-crosslinker solution of 0.001 parts by weight of acid esters heats 45 minutes or so so that institute at 200 DEG C The CRC of obtained absorbent resin powder (5) is 32g/g.Then operation same as Example 4 is carried out, graininess suction is obtained Aqua (5).The various physical property of particulate water-absorbing agent (5) are as shown in table 3~6.
[embodiment 6]
(gel crushing)
Aqueous gel (4) obtained in above-mentioned Production Example 4 is supplied to screw extruder and carries out gel crushing.As the spiral shell Bar extruder has diameter 100mm, aperture 6.4mm, hole count 83, percent opening 41.4%, thickness 10mm using in front end The masticator of the outer diameter 86mm of the screw shaft of porous plate.In the state that the screw shaft revolving speed of the masticator is 130rpm, with 4640 [g/ minutes] supply aqueous gels (4), while with 83 [g/ minutes] supply vapor.Gel size reduction energy at this time It (GGE) be 29.5 [J/g], GGE (2) is 15.7 [J/g].It should be noted that the temperature of the aqueous gel (4) before gel crushing Be 80 DEG C, gel it is smashed crush gel, i.e. graininess aqueous gel (6) temperature be increased to 86 DEG C.
Graininess aqueous gel (6) obtained in above-mentioned gel pulverizing process is 46.5 weight % of resin solid content, again The logstandard deviation (σ ζ) 0.99 of equal 360 μm of partial size (D50), size distribution.The condition of the gel pulverizing process such as 1 institute of table Show, the physical property of graininess aqueous gel (6) it is as shown in table 2.
(drying)
Then above-mentioned graininess aqueous gel (6) is spread on vent board (this within 1 minute after gel crushes When the temperature of graininess aqueous gel (6) be 80 DEG C), carry out drying in 30 minutes at 185 DEG C, obtain dry polymer (6).Heat The mean wind speed of wind relative to zone of aeration direction of travel vertical direction be 1.0 [m/s].It should be noted that the wind of hot wind Speed utilizes Kanomax Japan, Inc. steady temperature hot type airspeedometer Anemomaster 6162 to measure.
(crushing and classification)
Then, dry polymer obtained in above-mentioned drying process (6) total amount is supplied to triple-roller mill and is crushed (crushing Process), it then and then with the JIS standard screen in 710 μm and 175 μm of aperture is classified, thus obtains the suction of unsetting broken shape Water-base resin particle (6).Water-absorbent besin particles (6) are the logstandard deviation of 351 μm of weight average particle diameter (D50), size distribution (σ ζ) 0.32, CRC 39.3 [g/g], 150 μm pass through particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) 0.4 weight %.
(surface treating additive addition)
It uniformly mixes sequentially for above-mentioned (6) 100 parts by weight of water-absorbent besin particles comprising ethylene glycol diglycidyl base (the covalent bond of 0.025 parts by weight of ether, 3.0 parts by weight of 0.4 parts by weight of ethylene carbonate, 0.6 parts by weight of propylene glycol and deionized water Conjunction property) surface-crosslinker solution, heats 30 minutes or so at 190 DEG C so that obtained absorbent resin powder (6) CRC be 34~35g/g.Then it is cooled down, implements the test of above-mentioned coating mixing machine, assign the damage for being equivalent to manufacturing process Later, 100 parts by weight of water-absorbent besin particles are equably mixed comprising 1 parts by weight of water, 5 acetic acid of diethylenetriamines, 3 sodium The aqueous solution of 0.01 parts by weight.At 60 DEG C after drying 1 hour, by 710 μm of the JIS standard screen in aperture, dioxy is equably added SiClx (trade name: Aerosil 200, Nippon Aerosil Co., Ltd. system) 0.4 parts by weight.So obtain graininess suction Aqua (6).The various physical property of particulate water-absorbing agent (6) are as shown in table 3~6.It should be noted that after paint mixer test 150 μm when further implementing particulate water-absorbing agent paint mixer test by the expression of particle incrementss (assuming that diaper etc. Absorber manufacture when process-induced damage) 150 μm of incrementss by particle.
[embodiment 7]
Operation same as Example 6 is carried out other than operation as shown below.Using obtained in above-mentioned Production Example 5 Aqueous gel (5) substitutes aqueous gel (4).Gel size reduction energy (GGE) at this time is 34.5 [J/g], GGE (2) is 19.6 [J/g].It should be noted that gel crush before aqueous gel (5) temperature be 80 DEG C, the smashed crushing gel of gel, That is the temperature of graininess aqueous gel (7) is increased to 87 DEG C.
Graininess aqueous gel (7) obtained in above-mentioned gel pulverizing process is 46.6 weight % of resin solid content, again The logstandard deviation (σ ζ) 1.02 of equal 627 μm of partial size (D50), size distribution.The condition of the gel pulverizing process such as 1 institute of table Show, the physical property of graininess aqueous gel (7) it is as shown in table 2.
Then drying and crushing progressive operation same as Example 6 is carried out, the water imbibition of unsetting broken shape is obtained Resin particle (7).Water-absorbent besin particles (7) are the logstandard deviation (σ ζ) of 366 μm of weight average particle diameter (D50), size distribution 0.32, CRC 49.4 [g/g], 150 μm pass through particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) 0.4 weight %.
It uniformly mixes sequentially for above-mentioned (7) 100 parts by weight of water-absorbent besin particles comprising ethylene glycol diglycidyl base (the covalent bond of 0.025 parts by weight of ether, 3.0 parts by weight of 0.4 parts by weight of 1,3- propylene glycol, 0.6 parts by weight of propylene glycol and deionized water Conjunction property) surface-crosslinker solution, heats 30 minutes or so at 190 DEG C so that obtained absorbent resin powder (7) CRC be 39~40g/g.Then operation similarly to Example 6 is carried out.So obtain particulate water-absorbing agent (7).Graininess is inhaled The various physical property of aqua (7) are as shown in table 3~6.
[embodiment 8]
Carry out the net in 710 μm of aperture used in alternate embodiment 6 using 850 μm of net, in addition to this carries out and embodiment 6 Identical operation.The obtained water-absorbent besin particles (8) are the logarithmic scale of 450 μm of weight average particle diameter (D50), size distribution Deviation (σ ζ) 0.32, CRC 39.5 [g/g], 150 μm by particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) be 0.1 Weight %.In addition, the various physical property of obtained particulate water-absorbing agent (8) are as shown in table 3~6.
[embodiment 9]
Carry out the net in 710 μm of aperture used in alternate embodiment 7 using 850 μm of net, in addition to this carries out and embodiment 7 Identical operation.The obtained water-absorbent besin particles (9) are the logarithmic scale of 448 μm of weight average particle diameter (D50), size distribution Deviation (σ ζ) 0.31, CRC 49.6 [g/g], 150 μm by particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) be 0.3 Weight %.In addition, the various physical property of obtained particulate water-absorbing agent (9) are as shown in table 3~6.
[embodiment 10]
Carry out the net in 710 μm of aperture used in alternate embodiment 6 using 750 μm of net, in addition to this carries out and embodiment 6 Identical operation.The obtained water-absorbent besin particles (10) are the logarithm mark of 392 μm of weight average particle diameter (D50), size distribution Quasi- deviation (σ ζ) 0.36, CRC 39.5 [g/g], 150 μm be by particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) 0.3 weight %.
Obtained (10) 100 parts by weight of water-absorbent besin particles are uniformly mixed comprising 0.3 weight of ethylene carbonate (covalently bonded) surface-crosslinker solution for measuring part, 2.0 parts by weight of 0.5 parts by weight of propylene glycol and deionized water, at 200 DEG C Heat treatment 45 minutes or so is so that the CRC of obtained absorbent resin powder (10) is 31~32g/g.Then it carries out cold But, implement the test of above-mentioned coating mixing machine, imparting is equivalent to after the damage of manufacturing process, for water-absorbent besin particles 100 Parts by weight equably mix the aqueous solution comprising 0.5 parts by weight of water, 0.05 parts by weight of polyethylene glycol (average molecular weight 400), into And it equably mixes comprising 5 acetic acid of diethylenetriamines, 3 sodium, 0.01 parts by weight, 27.5 weight % aluminum sulfate aqueous solutions (according to oxygen Change aluminium be 8 weight %) 0.6 parts by weight, 60 weight % sodium lactate aqueous solution, 0.1 parts by weight, 0.02 parts by weight of propylene glycol it is water-soluble Liquid.At 60 DEG C after drying 1 hour, pass through 750 μm of the sieve in aperture.So obtain particulate water-absorbing agent (10).Particulate water-absorbing agent (10) various physical property are as shown in table 3~6.
[embodiment 11-1]
(2) 100 parts by weight of water-absorbent besin particles obtained in embodiment 2 are uniformly mixed and are shunk comprising ethylene glycol two 0.025 parts by weight of glyceryl ether, 0.4 parts by weight of ethylene carbonate, 0.6 parts by weight of propylene glycol and deionized water 3.0 parts by weight (covalently bonded) surface-crosslinker solution heats 40 minutes or so so that obtained water-absorbing resins at 175 DEG C The CRC of powder (11-1) is 38~40g/g.Then it is cooled down, implements the test of above-mentioned coating mixing machine, imparting is equivalent to manufacture After the damage of technique, 100 parts by weight of water-absorbent besin particles are equably mixed comprising 1 parts by weight of water, diethylidene three The aqueous solution of 5 acetic acid of amine, 3 sodium, 0.01 parts by weight.At 60 DEG C after drying 1 hour, by 710 μm of the JIS standard screen in aperture, uniformly Ground mixing hydrotalcite (ProductName: DHT-6, Kyowa Chemical Industry Co., Ltd's system, Mg6Al2(OH)16CO3·4H2O [general formula (1) X=0.25, m=0.50], 0.5 μm of volume average particle size) 0.3 parts by weight.So obtain particulate water-absorbing agent (11-1).? The various physical property of particulate water absorbent containing (11-1) are as shown in table 3~5.It should be noted that 150 μm after paint mixer test are logical It crosses when paint mixer test is further implemented particulate water-absorbing agent in the expression of particle incrementss (assuming that the absorber of diaper etc. Process-induced damage when manufacture) 150 μm of incrementss by particle.In addition, the neatly obtained using XRD determining in water absorbing agent The content of stone is 0.3 weight %.Additionally, there are being put down using what granulometry obtained in the hydrotalcite on above-mentioned water absorbing agent surface Equal partial size is 0.5 μm.
[embodiment 11-2]
Mix hydrotalcite (ProductName HT-1-NC, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4Al2(OH)12CO3· 3H2O [x=0.33, m=0.5 of general formula (1)], 0.58 μm of volume average particle size) 0.3 parts by weight come alternate embodiment 11-1's Hydrotalcite (ProductName DHT-6), is in addition to this similarly operated.So obtain particulate water-absorbing agent (11-2).Graininess The various physical property of water absorbing agent (11-2) are as shown in table 3~5.In addition, the hydrotalcite obtained using XRD determining in water absorbing agent is contained Amount is 0.3 weight %.Additionally, there are in the average grain diameter of the hydrotalcite on above-mentioned water absorbing agent surface obtained using granulometry It is 0.58 μm.
[embodiment 11-3]
Mix hydrotalcite (ProductName HT-P, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4.5Al2(OH)13CO3· 3.5H2O [x=0.69, m=0.54 of general formula (1)], 0.45 μm of volume average particle size) 0.3 parts by weight carry out alternate embodiment 11-1 Hydrotalcite (ProductName DHT-6), in addition to this similarly operated.So obtain particulate water-absorbing agent (11-3).Particle The various physical property of shape water absorbing agent (11-3) are as shown in table 3~5.In addition, the hydrotalcite obtained using XRD determining in water absorbing agent Content is 0.3 weight %.Additionally, there are in the average grain of the hydrotalcite on above-mentioned water absorbing agent surface obtained using granulometry Diameter is 0.45 μm.
[embodiment 11-4]
Mixed phosphate tricalcium (Wako Pure Chemical Industries, Ltd.'s system, CAS No.7758-87-4) 0.5 parts by weight substitute The hydrotalcite (ProductName DHT-6) of embodiment 11-1, is in addition to this similarly operated.So obtain particulate water-absorbing agent (11-4).The various physical property of particulate water-absorbing agent (11-4) are as shown in table 3~5.Additionally, there are on above-mentioned water absorbing agent surface Tricalcium phosphate be 0.04 μm using the crystallite diameter that granulometry obtains, average primary particle diameter is 0.04 μm.
[embodiment 11-5]
The surface treatment condition of embodiment 11-1 changes as described below.
(2) 100 parts by weight of water-absorbent besin particles are uniformly mixed comprising 0.030 weight of ethylene glycol diglycidyl base ether (covalently bonded) surface-crosslinker solution for measuring part, 3.0 parts by weight of 1.0 parts by weight of propylene glycol and deionized water, at 100 DEG C Heat treatment 45 minutes or so is so that the CRC of obtained absorbent resin powder (11-5) is 35~36g/g.Then it carries out cold But, implement the test of above-mentioned coating mixing machine, imparting is equivalent to after the damage of manufacturing process, for water-absorbent besin particles 100 Parts by weight equably mix the aqueous solution comprising 1 parts by weight of water, 5 acetic acid of diethylenetriamines, 3 sodium, 0.01 parts by weight.It is done at 60 DEG C After dry 1 hour, by 710 μm of the JIS standard screen in aperture, hydrotalcite (ProductName: DHT-6, consonance chemical industry is equably mixed Co. Ltd. system, Mg6Al2(OH)16CO3·4H2O [x=0.25, m=0.50 of general formula (1)], 0.5 μm of volume average particle size) 0.3 parts by weight.So obtain particulate water-absorbing agent (11-5).The various physical property of particulate water-absorbing agent (11-5) such as 3~5 institute of table Show.It should be noted that 150 μm after paint mixer test are indicated for particulate water-absorbing agent by particle incrementss into one Step implements 150 μm of increasings by particle of (assuming that process-induced damage when the absorber manufacture of diaper etc.) when paint mixer test Dosage.
[embodiment 11-6]
Mix hydrotalcite (ProductName HT-1-NC, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4Al2(OH)12CO3· 3H2O [x=0.33, m=0.5 of general formula (1)], 0.58 μm of volume average particle size) 0.3 parts by weight come alternate embodiment 11-5's Hydrotalcite (ProductName DHT-6), is in addition to this similarly operated.So obtain particulate water-absorbing agent (11-6).Graininess The various physical property of water absorbing agent (11-6) are as shown in table 3~5.
[embodiment 11-7]
Mix hydrotalcite (ProductName HT-P, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4.5Al2(OH)13CO3· 3.5H2O [x=0.69, m=0.54 of general formula (1)], 0.45 μm of volume average particle size) 0.3 parts by weight carry out alternate embodiment 11-5 Hydrotalcite (ProductName DHT-6), in addition to this similarly operated.So obtain particulate water-absorbing agent (11-7).Particle The various physical property of shape water absorbing agent (11-7) are as shown in table 3~5.
[embodiment 11-8]
Mixed phosphate tricalcium (Wako Pure Chemical Industries, Ltd.'s system, CAS No.7758-87-4) 0.5 parts by weight substitute The hydrotalcite (ProductName DHT-6) of embodiment 11-5, is in addition to this similarly operated.So obtain particulate water-absorbing agent (11-8).The various physical property of particulate water-absorbing agent (11-8) are as shown in table 3~5.
[embodiment 12-1]
Table identical with embodiment 11-1 is carried out for (7) 100 parts by weight of water-absorbent besin particles obtained in embodiment 7 The addition operation of surface treatment additive.So obtain particulate water-absorbing agent (12-1).The various objects of particulate water-absorbing agent (12-1) Property is as shown in table 3~5.
[embodiment 12-2]
Mix hydrotalcite (ProductName HT-1-NC, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4Al2(OH)12CO3· 3H2O [x=0.33, m=0.5 of general formula (1)], 0.58 μm of volume average particle size) 0.3 parts by weight come alternate embodiment 12-1's Hydrotalcite (ProductName DHT-6), is in addition to this similarly operated.So obtain particulate water-absorbing agent (12-2).Graininess The various physical property of water absorbing agent (12-2) are as shown in table 3~5.
[embodiment 12-3]
Mix hydrotalcite (ProductName HT-P, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4.5Al2(OH)13CO3· 3.5H2O [x=0.69, m=0.54 of general formula (1)], 0.45 μm of volume average particle size) 0.3 parts by weight carry out alternate embodiment 12-1 Hydrotalcite (ProductName DHT-6), in addition to this similarly operated.So obtain particulate water-absorbing agent (12-3).Particle The various physical property of shape water absorbing agent (12-3) are as shown in table 3~5.
[embodiment 12-4]
Mixed phosphate tricalcium (Wako Pure Chemical Industries, Ltd.'s system, CAS No.7758-87-4) 0.5 parts by weight substitute The hydrotalcite (ProductName DHT-6) of embodiment 12-1, is in addition to this similarly operated.So obtain particulate water-absorbing agent (12-4).The various physical property of particulate water-absorbing agent (12-4) are as shown in table 3~5.
[embodiment 12-5]
The surface treatment condition of embodiment 12-1 changes as described below.
(7) 100 parts by weight of water-absorbent besin particles are uniformly mixed comprising 0.030 weight of ethylene glycol diglycidyl base ether (covalently bonded) surface-crosslinker solution for measuring part, 3.0 parts by weight of 1.0 parts by weight of propylene glycol and deionized water, at 100 DEG C Heat treatment 45 minutes or so is so that the CRC of obtained absorbent resin powder (12-5) is 35~36g/g.Then it carries out cold But, implement the test of above-mentioned coating mixing machine, imparting is equivalent to after the damage of manufacturing process, for water-absorbent besin particles 100 Parts by weight equably mix the aqueous solution comprising 1 parts by weight of water, 5 acetic acid of diethylenetriamines, 3 sodium, 0.01 parts by weight.It is done at 60 DEG C After dry 1 hour, by 710 μm of the JIS standard screen in aperture, hydrotalcite (ProductName: DHT-6, consonance chemical industry is equably mixed Co. Ltd. system, Mg6Al2(OH)16CO3·4H2O [x=0.25, m=0.50 of general formula (1)], 0.5 μm of volume average particle size) 0.3 parts by weight.So obtain particulate water-absorbing agent (12-5).The various physical property of particulate water-absorbing agent (12-5) such as 3~5 institute of table Show.It should be noted that 150 μm after paint mixer test are indicated for particulate water-absorbing agent by particle incrementss into one Step implements 150 μm of increasings by particle of (assuming that process-induced damage when the absorber manufacture of diaper etc.) when paint mixer test Dosage.
[embodiment 12-6]
Mix hydrotalcite (ProductName HT-1-NC, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4Al2(OH)12CO3· 3H2O [x=0.33, m=0.5 of general formula (1)], 0.58 μm of volume average particle size) 0.3 parts by weight come alternate embodiment 12-5's Hydrotalcite (ProductName DHT-6), is in addition to this similarly operated.So obtain particulate water-absorbing agent (12-6).Graininess The various physical property of water absorbing agent (12-6) are as shown in table 3~5.
[embodiment 12-7]
Mix hydrotalcite (ProductName HT-P, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4.5Al2(OH)13CO3· 3.5H2O [x=0.69, m=0.54 of general formula (1)], 0.45 μm of volume average particle size) 0.3 parts by weight carry out alternate embodiment 12-5 Hydrotalcite (ProductName DHT-6), in addition to this similarly operated.So obtain particulate water-absorbing agent (12-7).Particle The various physical property of shape water absorbing agent (12-7) are as shown in table 3~5.
[embodiment 12-8]
Mixed phosphate tricalcium (Wako Pure Chemical Industries, Ltd.'s system, CAS No.7758-87-4) 0.5 parts by weight substitute The hydrotalcite (ProductName DHT-6) of embodiment 12-5, is in addition to this similarly operated.So obtain particulate water-absorbing agent (12-8).The various physical property of particulate water-absorbing agent (12-8) are as shown in table 3~5.
[embodiment 13-1]
Table identical with embodiment 11-4 is carried out for (1) 100 parts by weight of water-absorbent besin particles obtained in embodiment 1 The addition operation of surface treatment additive.So obtain particulate water-absorbing agent (13-1).The various objects of particulate water-absorbing agent (13-1) Property is as shown in table 3~5.
[embodiment 13-2]
The surface treatment condition of embodiment 13-1 changes as described below.
Surface treating additive identical with embodiment 11-5 is carried out for (1) 100 parts by weight of water-absorbent besin particles Addition operation.So obtain particulate water-absorbing agent (13-2).The various physical property of particulate water-absorbing agent (13-2) are as shown in table 3~5.
[embodiment 14]
Table identical with embodiment 11-5 is carried out for (3) 100 parts by weight of water-absorbent besin particles obtained in embodiment 3 The addition operation of surface treatment additive.So obtain particulate water-absorbing agent (14).The various physical property of particulate water-absorbing agent (14) are such as Shown in table 3~5.
[embodiment 15]
Carry out the net in 710 μm of aperture used in alternate embodiment 11-1 using 750 μm of net, in addition to this carry out and implements The identical gel of example 11-1 crushes drying and crushing progressive operation.The obtained water-absorbent besin particles (15) are attached most importance to 385 μm of partial size (D50), logstandard deviation (σ ζ) 0.35, CRC 48.3 [g/g] of size distribution, 150 μm it is (logical by particle Cross the ratio of the particle of the sieve in 150 μm of aperture) it is 0.3 weight %.
Surface treatment identical with embodiment 11-6 is carried out sequentially for (15) 100 parts by weight of water-absorbent besin particles to add Add agent addition operation.So obtain particulate water-absorbing agent (15).The various physical property of particulate water-absorbing agent (15) are as shown in table 3~5.
[embodiment 16]
Carry out the net in 710 μm of aperture used in alternate embodiment 13-1 using 850 μm of net, in addition to this carry out and implements The identical gel of example 13-1 crushes drying and crushing progressive operation.The obtained water-absorbent besin particles (16) are attached most importance to 428 μm of partial size (D50), logstandard deviation (σ ζ) 0.35, CRC 42.8 [g/g] of size distribution, 150 μm it is (logical by particle Cross the ratio of the particle of the sieve in 150 μm of aperture) it is 0.3 weight %.
Surface treatment identical with embodiment 11-7 is carried out sequentially for (16) 100 parts by weight of water-absorbent besin particles to add Add agent addition operation.So obtain particulate water-absorbing agent (16).The various physical property of particulate water-absorbing agent (16) are as shown in table 3~5.
[embodiment 17]
Carry out the net in 710 μm of aperture used in alternate embodiment 13-1 using 750 μm of net, in addition to this carry out and implements The identical gel of example 13-1 crushes drying and crushing progressive operation.The obtained water-absorbent besin particles (17) are attached most importance to 386 μm of partial size (D50), logstandard deviation (σ ζ) 0.35, CRC 42.6 [g/g] of size distribution, 150 μm it is (logical by particle Cross the ratio of the particle of the sieve in 150 μm of aperture) it is 0.3 weight %.
Surface treatment identical with embodiment 11-8 is carried out sequentially for (17) 100 parts by weight of water-absorbent besin particles to add Add agent addition operation.So obtain particulate water-absorbing agent (17).The various physical property of particulate water-absorbing agent (17) are as shown in table 3~5.
[embodiment 18]
(gel crushing)
Aqueous gel (6) obtained in above-mentioned Production Example 6 is supplied to screw extruder and carries out gel crushing.As the spiral shell Bar extruder, using front end have diameter 100mm, aperture 8mm, hole count 54, thickness 10mm porous plate screw shaft Outer diameter 86mm masticator.In the state that the screw shaft revolving speed of the masticator is 130rpm, supplied within [g/ minutes] with 4640 Aqueous gel (6), while with 83 [g/ minutes] supply vapor.Gel size reduction energy (GGE) at this time is 32.3 [J/g], GGE It (2) is 17.8 [J/g].It should be noted that the temperature of the aqueous gel (6) before gel crushing is 80 DEG C, gel is smashed Crush gel, i.e. the temperature of graininess aqueous gel (18) is increased to 84 DEG C.
Graininess aqueous gel (18) obtained in above-mentioned gel pulverizing process is 47.5 weight % of resin solid content, again The logstandard deviation (σ ζ) 0.94 of equal 820 μm of partial size (D50), size distribution.The condition of the gel pulverizing process such as 1 institute of table Show, the physical property of graininess aqueous gel (18) it is as shown in table 2.
(drying)
Then above-mentioned graininess aqueous gel (18) is spread on vent board within 1 minute after gel crushes (temperature of graininess aqueous gel (18) at this time be 80 DEG C) carries out drying in 30 minutes at 185 DEG C, obtains dry polymer (18).The mean wind speed of hot wind relative to zone of aeration direction of travel vertical direction be 1.0 [m/s].It should be noted that hot The wind speed of wind utilizes Kanomax Japan, Inc. steady temperature hot type airspeedometer Anemomaster 6162 to measure.
(crushing and classification)
Then, dry polymer obtained in above-mentioned drying process (18) total amount is supplied to triple-roller mill and is crushed (powder Broken process), it then and then with the JIS standard screen in 710 μm and 175 μm of aperture is classified, thus obtains unsetting broken shape Water-absorbent besin particles (18).Water-absorbent besin particles (18) are the logarithmic scale of 356 μm of weight average particle diameter (D50), size distribution Deviation (σ ζ) 0.32, CRC 48.3 [g/g], 150 μm pass through particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) 0.4 weight Measure %.
(surface treating additive addition)
It uniformly mixes sequentially for above-mentioned (18) 100 parts by weight of water-absorbent besin particles comprising ethylene glycol diglycidyl base (the covalent bond of 0.025 parts by weight of ether, 3.0 parts by weight of 0.4 parts by weight of ethylene carbonate, 0.6 parts by weight of propylene glycol and deionized water Conjunction property) surface-crosslinker solution, heats 30 minutes or so at 190 DEG C so that obtained absorbent resin powder (18) CRC be 38~39g/g.Then it is cooled down, implements the test of above-mentioned coating mixing machine, assign the damage for being equivalent to manufacturing process Later, 100 parts by weight of water-absorbent besin particles are equably mixed comprising 1 parts by weight of water, 5 acetic acid of diethylenetriamines, 3 sodium The aqueous solution of 0.01 parts by weight.At 60 DEG C after drying 1 hour, by 710 μm of the JIS standard screen in aperture, dioxy is equably added SiClx (trade name: Aerosil 200, Nippon Aerosil Co., Ltd. system) 0.4 parts by weight.So obtain graininess suction Aqua (18).The various physical property of particulate water-absorbing agent (18) are as shown in table 3~5.It should be noted that after paint mixer test 150 μm when further implementing paint mixer test for particulate water-absorbing agent by the expression of particle incrementss (assuming that diaper Deng absorber manufacture when process-induced damage) 150 μm of incrementss by particle.
[embodiment 19]
Dry polymer obtained in embodiment 18 (18) total amount is supplied to triple-roller mill and is crushed (pulverizing process), so It is classified afterwards and then with the sieve in 850 μm and 256 μm of aperture, thus obtains the water-absorbent besin particles of unsetting broken shape (19).Water-absorbent besin particles (19) be 447 μm of weight average particle diameter (D50), size distribution logstandard deviation (σ ζ) 0.29, CRC 48.8 [g/g], 150 μm pass through particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) 0.2 weight %.
Carry out with the water-absorbent besin particles (18) for embodiment 18 sequentially for water-absorbent besin particles (19) The identical operation of operation.So obtain particulate water-absorbing agent (19).The various physical property of particulate water-absorbing agent (19) such as table 3~5 It is shown.It should be noted that paint mixer test after 150 μm by particle incrementss indicate for particulate water-absorbing agent into One step implements 150 μm of (assuming that process-induced damage when the absorber manufacture of diaper etc.) when paint mixer test by particle Incrementss.
[embodiment 20]
Operation same as Example 7 is carried out using aqueous gel (7) obtained in above-mentioned Production Example 7.Gel at this time Size reduction energy (GGE) is 35.2 [J/g], GGE (2) is 20.1 [J/g].It should be noted that the aqueous gel before gel crushing (7) temperature is 80 DEG C, the temperature of the smashed crushing gel of gel, i.e. graininess aqueous gel (20) is increased to 86 DEG C.
Graininess aqueous gel (20) obtained in gel pulverizing process is 46.6 weight % of resin solid content, again equal grain The logstandard deviation (σ ζ) 0.97 of 601 μm of diameter (D50), size distribution.The condition of the gel pulverizing process as shown in table 1, The physical property of granular aqueous gel (20) is as shown in table 2.
By water-absorbent besin particles (20) obtained from the classification of graininess aqueous gel (20) drying and crushing, the equal grain of weight 360 μm of diameter (D50), the logstandard deviation (σ ζ) 0.32 of size distribution, CRC 49.6 [g/g], 150 μm (passed through by particle The ratio of the particle for the sieve that 150 μm of aperture) 0.3 weight %.
Water-absorbent besin particles (20) are carried out with surface treating additive addition same as Example 7, thus To particulate water-absorbing agent (20).The various physical property of particulate water-absorbing agent (20) are as shown in table 3~5.It should be noted that coating is mixed Conjunction machine test after 150 μm by particle incrementss expression further implement paint mixer test for particulate water-absorbing agent when 150 μm of incrementss by particle of (assuming that process-induced damage when the absorber manufacture of diaper etc.).
[embodiment 21-1]
(18) 100 parts by weight of water-absorbent besin particles obtained in embodiment 18 are uniformly mixed and are contracted comprising ethylene glycol two 0.025 parts by weight of water glyceryl ether, 3.0 parts by weight of 0.4 parts by weight of ethylene carbonate, 0.6 parts by weight of propylene glycol and deionized water (covalently bonded) surface-crosslinker solution, heat 40 minutes or so at 175 DEG C so that obtained water imbibition tree The CRC at cosmetics end (21) is 38~39g/g.Then it is cooled down, implements the test of above-mentioned coating mixing machine, imparting is equivalent to manufacture After the damage of technique, 100 parts by weight of water-absorbent besin particles are equably mixed comprising 1 parts by weight of water, diethylidene three The aqueous solution of 5 acetic acid of amine, 3 sodium, 0.01 parts by weight.At 60 DEG C after drying 1 hour, by 710 μm of the JIS standard screen in aperture, uniformly Ground mixing hydrotalcite (ProductName: DHT-6, Kyowa Chemical Industry Co., Ltd's system, Mg6Al2(OH)16CO3·4H2O [general formula (1) X=0.25, m=0.50], 0.5 μm of volume average particle size) 0.3 parts by weight.So obtain particulate water-absorbing agent (21).Particle The various physical property of shape water absorbing agent (21-1) are as shown in table 3~5.It should be noted that 150 μm after paint mixer test pass through (assuming that the absorption system of diaper etc. when paint mixer test is further implemented particulate water-absorbing agent in the expression of particle incrementss Process-induced damage when making) 150 μm of incrementss by particle.In addition, the hydrotalcite obtained using XRD determining in water absorbing agent Content be 0.3 weight %.Additionally, there are being averaged using what granulometry obtained in the hydrotalcite on above-mentioned water absorbing agent surface Partial size is 0.5 μm.
[embodiment 21-2]
Mix hydrotalcite (ProductName HT-1-NC, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4Al2(OH)12CO3· 3H2O [x=0.33, m=0.5 of general formula (1)], 0.58 μm of volume average particle size) 0.3 parts by weight come alternate embodiment 21-1's Hydrotalcite (ProductName DHT-6), is in addition to this similarly operated.So obtain particulate water-absorbing agent (21-2).Graininess The various physical property of water absorbing agent (21-2) are as shown in table 3~5.In addition, the hydrotalcite obtained using XRD determining in water absorbing agent is contained Amount is 0.3 weight %.Additionally, there are in the average grain diameter of the hydrotalcite on above-mentioned water absorbing agent surface obtained using granulometry It is 0.58 μm.
[embodiment 21-3]
Mix hydrotalcite (ProductName HT-P, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4.5Al2(OH)13CO3· 3.5H2O [x=0.69, m=0.54 of general formula (1)], 0.45 μm of volume average particle size) 0.3 parts by weight carry out alternate embodiment 21-1 Hydrotalcite (ProductName DHT-6), in addition to this similarly operated.So obtain particulate water-absorbing agent (21-3).Particle The various physical property of shape water absorbing agent (21-3) are as shown in table 3~5.In addition, the hydrotalcite obtained using XRD determining in water absorbing agent Content is 0.3 weight %.Additionally, there are in the average grain of the hydrotalcite on above-mentioned water absorbing agent surface obtained using granulometry Diameter is 0.45 μm.
[embodiment 21-4]
Mixed phosphate tricalcium (Wako Pure Chemical Industries, Ltd.'s system, CAS No.7758-87-4) 0.5 parts by weight substitute The hydrotalcite (ProductName DHT-6) of embodiment 21-1, is in addition to this similarly operated.So obtain particulate water-absorbing agent (21-4).The various physical property of particulate water-absorbing agent (21-4) are as shown in table 3~5.Additionally, there are on above-mentioned water absorbing agent surface Tricalcium phosphate be 0.04 μm using the crystallite diameter that granulometry obtains, average primary particle diameter is 0.04 μm.
[embodiment 22-1]
Water-absorbent besin particles and surface treatment condition are changed to implement operation identical with embodiment 21-1.It is specific and Speech, water-absorbent besin particles (18) is substituted using water-absorbent besin particles obtained in embodiment 20 (20), and then at surface Manage bar part changes as described below.(20) 100 parts by weight of water-absorbent besin particles are uniformly mixed and are shunk comprising ethylene glycol two (covalently bonded) of 3.0 parts by weight of 0.030 parts by weight of glyceryl ether, 1.0 parts by weight of propylene glycol and deionized water is surface-crosslinked Agent solution, heat 45 minutes or so at 100 DEG C so that obtained absorbent resin powder (22) CRC be 35~ 36g/g.Then it is cooled down, implements the test of above-mentioned coating mixing machine, imparting is equivalent to after the damage of manufacturing process, for inhaling It includes 1 parts by weight of water, 5 acetic acid of diethylenetriamines, 3 sodium, 0.01 parts by weight that 100 parts by weight of water-base resin particle, which equably mix, Aqueous solution.At 60 DEG C after dry 1 hour, by 710 μm of the JIS standard screen in aperture, equably mix hydrotalcite (ProductName: DHT-6, Kyowa Chemical Industry Co., Ltd's system, Mg6Al2(OH)16CO3·4H2O [x=0.25, m=0.50 of general formula (1)], body 0.5 μm of average grain diameter of product) 0.3 parts by weight.So obtain particulate water-absorbing agent (22-1).Particulate water-absorbing agent (22-1) it is various Physical property is as shown in table 3~5.It should be noted that paint mixer test after 150 μm by particle incrementss indicate for Particulate water absorbent containing is further implemented the 150 of (assuming that process-induced damage when the absorber manufacture of diaper etc.) when paint mixer test μm pass through the incrementss of particle.
[embodiment 22-2]
Mix hydrotalcite (ProductName HT-1-NC, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4Al2(OH)12CO3· 3H2O [x=0.33, m=0.5 of general formula (1)], 0.58 μm of volume average particle size) 0.3 parts by weight come alternate embodiment 22-1's Hydrotalcite (ProductName DHT-6), is in addition to this similarly operated.So obtain particulate water-absorbing agent (22-2).Graininess The various physical property of water absorbing agent (22-2) are as shown in table 3~5.
[embodiment 22-3]
Mix hydrotalcite (ProductName HT-P, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4.5Al2(OH)13CO3· 3.5H2O [x=0.69, m=0.54 of general formula (1)], 0.45 μm of volume average particle size) 0.3 parts by weight carry out alternate embodiment 22-1 Hydrotalcite (ProductName DHT-6), in addition to this similarly operated.So obtain particulate water-absorbing agent (22-3).Particle The various physical property of shape water absorbing agent (22-3) are as shown in table 3~5.
[embodiment 22-4]
Mixed phosphate tricalcium (Wako Pure Chemical Industries, Ltd.'s system, CAS No.7758-87-4) 0.5 parts by weight substitute The hydrotalcite (ProductName DHT-6) of embodiment 22-1, is in addition to this similarly operated.So obtain particulate water-absorbing agent (22-4).The various physical property of particulate water-absorbing agent (22-4) are as shown in table 3~5.
[embodiment 23]
In embodiment 1, the heat treatment after (covalently bonded) surface-crosslinker solution in uniform mix embodiment 1 Time was changed to 45 minutes by 30 minutes, was in addition to this similarly operated.So obtain particulate water-absorbing agent (23).Particle The various physical property of shape water absorbing agent (23) are as shown in table 3~5.
[comparative example 1]
Operation same as Example 6 is carried out other than operation as shown below.Using obtained in above-mentioned Production Example 3 Aqueous gel (3) substitutes aqueous gel (4).The aperture of the porous plate of the front end of screw extruder is changed to 12.5mm.This When gel size reduction energy (GGE) be 19.4 [J/g], GGE (2) is 7.6 [J/g].It should be noted that containing before gel crushing The temperature of hydrogel (3) is 82 DEG C, the smashed temperature for crushing gel, comparing graininess aqueous gel (1) of gel increases To 84 DEG C.
Comparing graininess aqueous gel (1) obtained in above-mentioned gel pulverizing process is 52.6 weight of resin solid content Measure %, 1322 μm of weight average particle diameter (D50), size distribution logstandard deviation (σ ζ) 1.32.The condition of the gel pulverizing process As shown in table 1, the physical property for comparing graininess aqueous gel (1) is as shown in table 2.
Then, drying and crushing progressive operation same as Example 6 is carried out, the comparison for obtaining unsetting broken shape is inhaled Water-base resin particle (1).Compare the logarithmic scale that water-absorbent besin particles (1) is 350 μm of weight average particle diameter (D50), size distribution Deviation (σ ζ) 0.32, CRC 41.9 [g/g], 150 μm pass through particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) 0.5 weight Measure %.
Then compare water-absorbent besin particles (1) using above-mentioned, carry out surface treating additive same as Example 6 Addition.So obtain comparing particulate water-absorbing agent (1).Compare the various physical property of particulate water-absorbing agent (1) as shown in table 3~6.
[comparative example 2]
Using water-absorbent besin particles (1) is compared obtained in comparative example 1, carry out at surface same as in Example 10 Manage additive addition.So obtain comparing particulate water-absorbing agent (2).Compare the various physical property such as table 3 of particulate water-absorbing agent (2) Shown in~6.
[comparative example 3]
The net in 710 μm of aperture used in comparative example 1 is substituted using 850 μm of net, is in addition to this carried out and comparative example 1 Identical operation.Obtained relatively water-absorbent besin particles (3) are the logarithm of 431 μm of weight average particle diameter (D50), size distribution Standard deviation (σ ζ) 0.35, CRC 42.2 [g/g], 150 μm be by particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) 0.3 weight %.In addition, the various physical property of obtained relatively particulate water-absorbing agent (3) are as shown in table 3~6.
[comparative example 4]
Using comparing obtained in comparative example 1 graininess aqueous gel (1), drying identical with embodiment 11-1 is carried out Crushing and classification operation, obtains the comparison water-absorbent besin particles (4) of unsetting broken shape.Compare water-absorbent besin particles (4) For 350 μm of weight average particle diameter (D50), logstandard deviation (σ ζ) 0.32, CRC 41.9 [g/g] of size distribution, 150 μm by Grain (passing through the ratio of the particle of 150 μm of the sieve in aperture) is 0.5 weight %.
Then compare water-absorbent besin particles (4) using above-mentioned, carry out surface treatment identical with embodiment 11-1 and add Agent is added to add.So obtain comparing particulate water-absorbing agent (4).Compare various physical property such as 3~5 institute of table of particulate water-absorbing agent (4) Show.
[comparative example 5]
Mix hydrotalcite (ProductName HT-1-NC, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4Al2(OH)12CO3· 3H2O [x=0.33, m=0.5 of general formula (1)], 0.58 μm of volume average particle size) 0.3 parts by weight substitute the neatly of comparative example 4 Stone (ProductName DHT-6), is in addition to this similarly operated.So obtain comparing particulate water-absorbing agent (5).Compare graininess The various physical property of water absorbing agent (5) are as shown in table 3~5.
[comparative example 6]
Mix hydrotalcite (ProductName HT-P, Sakai Chemical Industry Co., Ltd.'s system, chemical formula Mg4.5Al2(OH)13CO3· 3.5H2O [x=0.69, m=0.54 of general formula (1)], 0.45 μm of volume average particle size) 0.3 parts by weight substitute comparative example 4 Hydrotalcite (ProductName DHT-6), is in addition to this similarly operated.So obtain comparing particulate water-absorbing agent (6).Compare The various physical property of particulate water absorbent containing (6) are as shown in table 3~5.
[comparative example 7]
Mixed phosphate tricalcium (Wako Pure Chemical Industries, Ltd.'s system, CAS No.7758-87-4) 0.5 parts by weight substitute The hydrotalcite (ProductName DHT-6) of comparative example 4, is in addition to this similarly operated.So obtain comparing particulate water-absorbing agent (7).Compare the various physical property of particulate water-absorbing agent (7) as shown in table 3~5.
[comparative example 8]
Operation same as Example 1 is carried out other than operation as shown below.Using obtained in above-mentioned Production Example 8 Aqueous gel (8) substitutes aqueous gel (1).The aperture of the porous plate of the front end of screw extruder is changed to 12.5mm.This When gel size reduction energy (GGE) be 19.1 [J/g], GGE (2) is 7.4 [J/g].It should be noted that containing before gel crushing The temperature of hydrogel (8) is 82 DEG C, the smashed temperature for crushing gel, comparing graininess aqueous gel (8) of gel increases To 84 DEG C.
Comparing graininess aqueous gel (8) obtained in above-mentioned gel pulverizing process is 52.6 weight of resin solid content Measure %, 1223 μm of weight average particle diameter (D50), size distribution logstandard deviation (σ ζ) 1.28.The condition of the gel pulverizing process As shown in table 1, the physical property for comparing graininess aqueous gel (8) is as shown in table 2.
Then, drying and crushing progressive operation same as Example 3 is carried out, the comparison for obtaining unsetting broken shape is inhaled Water-base resin particle (8).Compare the logarithmic scale that water-absorbent besin particles (8) are 426 μm of weight average particle diameter (D50), size distribution Deviation (σ ζ) 0.34, CRC 36.2 [g/g], 150 μm pass through particle (passing through the ratio of the particle of 150 μm of the sieve in aperture) 0.3 weight Measure %.
Then compare water-absorbent besin particles (8) using above-mentioned, carry out surface treating additive same as Example 1 Addition.So obtain comparing particulate water-absorbing agent (8).Compare the various physical property of particulate water-absorbing agent (8) as shown in table 3~5.
[table 1]
[table 2]
[table 3-1]
[table 3-2]
[table 4-1]
[table 4-2]
[table 5-1]
[table 5-2]
[table 5-3]
[table 6]
(analysis)
For above-described embodiment 1~23, comparative example 1~8, if DRC5 minute for being shown respectively in drafting table 3 and table 5 and again Equal partial size (D50) is then as shown in Figure 5.Linear was found between D50 at DRC5 minutes if observing embodiment 6~10.Compare It has also been found that identical linear in example 1~3 and Examples 1 to 5.It is interpreted as reducing for DRC5 minutes if D50 increases.
It is found that embodiment all has high DRC5 points if being compared for embodiment 6~10 and comparative example 1~3 Clock value.Embodiment 6~10 is the case where crushing the aqueous gel of the high moisture content of energy comminution with high gel, comparative example be with The case where low moisture content, low gel crushing energy comminution.Be interpreted as it is different according to the condition in gel pulverizing process and The physical property of particulate water absorbent containing changes.Examples 1 to 5 and comparative example 1~3 are compared and be will also realize that, Examples 1 to 5 is whole It is worth with high DRC5 minute.Examples 1 to 5 is to crush the high moisture content of energy comminution compared with comparative example with high gel The case where aqueous gel is result identical with embodiment 6~10.If comparing for Examples 1 to 5 and embodiment 6~10 Embodiment 6~10 known to more then is all worth with high DRC5 minute.Embodiment 6~10 and the different point of Examples 1 to 5 exist In using the aqueous gel of high moisture content.
As for by the particulate water-absorbing agent as the embodiment being all worth with high DRC5 minute, with such as comparative example The means for the particulate water-absorbing agent difference being all worth like that with low DRC5 minute, export DRC basic index as described above.
DRC basic index (Index of DRC)=(K-DRC5 minutes [g/g])/(D50 [μm]/1000)
(here, K is arbitrary constant).As representative examples, same as below in the case where using K=49.
In the case where K=49
DRC index (Index of DRC)=(49-DRC5 minutes [g/g])/(D50 [μm]/1000)
The value that the DRC index of embodiment 6~10 is 5~14, the DRC index of comparative example 1~3 is 43~46 on the other hand Value.It is understood to the difference of the particulate water-absorbing agent of embodiment and the particulate water-absorbing agent of comparative example.Examples 1 to 5 The value that DRC index is 16~25.By DRC index, it can easily be determined that the particulate water-absorbing agent with preferred physical property.
The value that the DRC index of embodiment 11-1~17 is 14~30, the DRC index of comparative example 4~7 is 49 on the other hand ~52 value.It is understood to the difference of the particulate water-absorbing agent of embodiment and the particulate water-absorbing agent of comparative example.These examples In, similarly by DRC index, it can easily be determined that the particulate water-absorbing agent with preferred physical property.
As shown in above-described embodiment 11-1~17, the particulate water-absorbing agent of the application has high crc value, high The B.R. value of AAP value, low DRC index and 0 weight %.On the other hand, in comparative example 4~7, DRC index is more than 49, is understood For without high water absorption speed.
As shown in 18~22-4 of above-described embodiment, comprising in the case where malic acid when polymerization, the graininess of the application Water absorbing agent also has the B.R. value of high crc value, high AAP value, low DRC index and 0 weight %.On the other hand, compare DRC index is more than 47 in example 8, is interpreted as not having high water absorption speed.
The heating treatment time after uniform mixing (covalently bonded) surface-crosslinker solution in embodiment 1 was by 30 minutes It is changed in 45 minutes embodiments 23, compared with Example 1, although CRC reduces 2.3g/g, AAP, diffusion absorption multiplying power 60 minutes, the value of diffusion absorption multiplying power 10 minutes and SFC increases.Those skilled in the art can set condition appropriate to obtain To the particulate water-absorbing agent with desired physical property.
Table 4 indicates the amount of bleeding back of the absorber made using each particulate water-absorbing agent.Use the particulate water-absorbing of embodiment In the case where agent, be 2.1g~4.9g value, on the other hand, using comparative example particulate water-absorbing agent the case where the amount of bleeding back 14.5g or more is shown.The amount of bleeding back for being interpreted as the particulate water-absorbing agent of the application is few, Re-wet is improved.
The graininess of the invention manufactured and crushing the aqueous gel of the high moisture content of energy comminution with high gel Water absorbing agent has excellent physical property.Centrifugal separator keeps capacity (CRC) to be 30~50g/g, be high water absorbent rate.Dipping is protected Hold capacity value (DRC5 minutes) 5 minutes for high value, reach high water absorption speed.6 institute of table as indicated the DRC5 minute of each granularity Show, each granularity all shows high DRC5 minute.Particulate water-absorbing agent of the invention is in turn in surface tension, grain shape, YI Value, coloring promote under the YI value after test, hygroscopic fluidity (B.R.), water soluble ingredient (Ext), deterioration soluble ingredient, pressurization Water absorbent rate (AAP), GCA (Gel Capillary Absorption), air entrapment rate, the examination of traumatic resistance paint mixer It tests, is one or more of physical property such as bulk density, diffusion absorption multiplying power 60 minutes, diffusion absorption multiplying power 10 minutes and the amount of bleeding back, excellent Choosing can all have excellent physical property.
Particulate water-absorbing agent of the invention as shown in the Examples, has high AAP value and low DRC index.This table Show, particulate water-absorbing agent of the invention has both high water absorption multiplying power and high water absorption speed, and it is excellent can to provide high lower water absorption of pressurizeing Particulate water-absorbing agent.In turn, particulate water-absorbing agent of the invention shows low B.R. value, also shows that hygroscopic fluidity is excellent. The present invention can provide the previous not getable agglomeration having both under high water absorption multiplying power and high water absorption speed, super-humid conditions and inhibit (hygroscopic fluidity) and/or the high excellent particulate water-absorbing agent of lower water absorption that pressurizes.
As described above, the present invention is illustrated using the preferred embodiment of the present invention, it is understood that should be only for the present invention Its range is explained by patent claims.It is interpreted as the patent quoted in this specification, patent application and other documents, Should its content itself in the same manner as specific in this specification is recorded using its content as the reference introduction for this specification. The application is for Japan filed in Japan's Patent 2016-63763 filed on March 28th, 2016, on September 30th, 2016 Japan's Patent 2016-194922 CLAIM OF PRIORITY filed in Patent No. 2016-194921 and on September 30th, 2016 is complete Portion's content is used as with reference to introduction in the application.
Industrial availability
According to the present invention it is possible to the excellent particulate water-absorbing agent for having both high water absorption multiplying power and high water absorption speed is provided, this Invention can be used in the various necks such as the hygienic materials such as paper nappy, sanitary napkin and then pet sheet material, sealing material Domain.

Claims (19)

1. a kind of particulate water-absorbing agent is the particulate water-absorbing agent that centrifugal separator keeps capacity (CRC) as 30~50g/g,
Weight average particle diameter (D50) is 200~600 μm,
DRC index shown in the following formula be 43 hereinafter,
DRC index (Index of DRC)=(49-DRC5 minutes [g/g])/(D50 [μm]/1000).
2. particulate water-absorbing agent according to claim 1, wherein the DRC index is 30 or less.
3. particulate water-absorbing agent described according to claim 1~any one of 2, wherein the DRC index is 20 or less.
4. particulate water-absorbing agent described in any one of claim 1 to 3, wherein saline flow conductivity (SFC) is 0 ~less than 30 (× 10-7·cm3·s·g-1)。
5. particulate water-absorbing agent according to any one of claims 1 to 4, wherein surface tension is 66mN/m or more.
6. particulate water-absorbing agent according to any one of claims 1 to 5, wherein grain shape is unsetting broken shape.
7. particulate water-absorbing agent described according to claim 1~any one of 6, wherein hygroscopic fluidity (B.R.) is 50 weights Measure % or less.
8. particulate water-absorbing agent according to any one of claims 1 to 7, wherein water soluble ingredient (Ext) is 25 weights Measure % or less.
9. particulate water-absorbing agent described according to claim 1~any one of 8, wherein deterioration soluble ingredient is 30 weight % Below.
10. particulate water-absorbing agent described according to claim 1~any one of 9, wherein water absorbent rate (AAP) is under pressurizeing 18g/g or more.
11. particulate water-absorbing agent described according to claim 1~any one of 10, wherein water absorbent rate (AAP) is under pressurizeing 26g/g or more.
12. particulate water-absorbing agent described according to claim 1~any one of 11, wherein internal gas as defined in following formula Bubble rate is 0.5~2.5%,
(air entrapment rate [%])={ (real density [g/cm3])-(apparent density [g/cm3])/(real density [g/cm3])× 100。
13. particulate water-absorbing agent described according to claim 1~any one of 12, wherein bulk density is 0.57~0.75.
14. particulate water-absorbing agent described according to claim 1~any one of 13, wherein be within diffusion absorption multiplying power 60 minutes 18g/g or more.
15. particulate water-absorbing agent described according to claim 1~any one of 14, wherein be within diffusion absorption multiplying power 10 minutes 7g/g or more.
16. polyacrylic acid (salt) is water imbibition tree by particulate water-absorbing agent described according to claim 1~any one of 15 Rouge is as main component.
17. particulate water-absorbing agent described according to claim 1~any one of 16 also contains selected from by with hydrotalcite knot 2 containing the divalent and trivalent kind metal cation of structure and the multi-element metal compound of hydroxyl and the anion comprising phosphoric acid class Improve at least one of the group of the water-insoluble metal phosphate of divalent or the metal cation of trivalent composition hygroscopic fluidity Agent.
18. a kind of absorber contains particulate water-absorbing agent described in any one of claim 1~17.
19. a kind of hygienic article contains the absorber described in claim 18.
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